Plasmon-Enhanced Ultraviolet Luminescence in Colloid Solutions and Nanostructures Based on Aluminum and ZnO Nanoparticles.

Aluminum nanoparticles attract scientific interest as a promising low-cost material with strong plasmon resonance in the ultraviolet region, which can be used in various fields of photonics. In this paper, for the first time, ultraviolet luminescence of zinc oxide nanoparticles in colloid solutions and nanostructure films in the presence of plasmonic aluminum nanoparticles 60 nm in size with a metal core and an aluminum oxide shell were studied. Mixture colloids of ZnO and Al nanoparticles in isopropyl alcohol solution with concentrations from 0.022 to 0.44 g/L and 0.057 to 0.00285 g/L, correspondingly, were investigated. The enhancement of up to 300% of ZnO emission at 377 nm in colloids mixtures with metal nanoparticles due to formation of Al-ZnO complex agglomerates was achieved. Plasmon nanostructures with different configurations of layers, such as Al on the surface of ZnO, ZnO on Al, sandwich-like structure and samples prepared from a colloidal mixture of ZnO and Al nanoparticles, were fabricated by microplotter printing. We demonstrated that photoluminescence can be boosted 2.4-fold in nanostructures prepared from a colloidal mixture of ZnO and Al nanoparticles, whereas the sandwich-like structure gave only 1.1 times the amplification of luminescence. Calculated theoretical models of photoluminescence enhancement of ideal and weak emitters near aluminum nanoparticles of different sizes showed comparable results with the obtained experimental data.

Engineering of the Photon Local Density of States: Strong Inhibition of Spontaneous Emission near the Resonant and High-Refractive Index Dielectric Nano-objects.

Metallic or dielectric nano-objects change the photon local density of states of closely placed emitters, particularly when plasmon or Mie resonances are present. Depending on the shape and material of these nano-objects, they may induce either a decrease or an increase in decay rates of the excited states of the emitter. In this work, we consider the reduction of the probability of optical transitions in emitters near high-refractive index dielectric (silicon and zinc selenide) nanoparticles. We tune the spectral positions of magnetic and electric modes of nanocylinders to obtain the largest overlap of the valleys in the total decay rate spectra for differently oriented dipoles and, in this way, find the highest inhibition of about 80% for randomly oriented emitters. The spectral positions of these valleys are easy to control since the wavelengths of the modes depend on the height and diameter of nanocylinders. The inhibition value is robust to the distance between the emitter and the nanoparticle in the range of nearly 50 nm, which is crucially important for the applications, such as selective optical transition engineering and photovoltaics.

Plasmon-enhanced fluorescence in gold nanorod-quantum dot coupled systems.

Plasmon-exciton coupling is of great importance to many optical devices and applications. One of the coupling manifestations is plasmon-enhanced fluorescence. Although this effect is demonstrated in numerous experimental and theoretical works, there are different particle shapes for which this effect is not fully investigated. In this work electrostatic complexes of gold nanorods and CdSe/CdZnS quantum dots were studied. Double-resonant gold nanorods have an advantage of the simultaneous enhancement of the absorption and emission when the plasmon bands match the excitation and fluorescence wavelengths of an emitter. A relationship between the concentration of quantum dots in the complexes and the enhancement factor was established. It was demonstrated that the enhancement factor is inversely proportional to the concentration of quantum dots. The maximal fluorescence enhancement by 10.8 times was observed in the complex with the smallest relative concentration of 2.5 quantum dots per rod and approximately 5 nm distance between them. Moreover, the influence of quantum dot location on the gold nanorod surface plays an important role. Theoretical study and experimental data indicate that only the position near the nanorod ends provides the enhancement. At the same time, the localization of quantum dots on the sides of the nanorods leads to the fluorescence quenching.

Possible nanoantenna control of chlorophyll dynamics for bioinspired photovoltaics.

In the context of using portions of a photosynthetic apparatus of green plants and photosynthesizing bacteria in bioinspired photovoltaic systems, we consider possible control of the chlorophyll excited state decay rate using nanoantennas in the form of a single metal and semiconductor nanoparticle. Since chlorophyll luminescence competes with electron delivery for chemical reactions chain and also to an external circuit, we examine possible excited state decay inhibition contrary to radiative rate enhancement. Both metal and semiconductor nanoparticles enable inhibition of radiative decay rate by one order of the magnitude as compared to that in vacuum, whereas a metal nanosphere cannot perform the overall decay inhibition since slowing down of radiative decay occurs only along with the similar growth of its nonradiative counterpart whereas a semiconductor nanoantenna is lossless. Additionally, at normal orientation of the emitter dipole moment to a nanoparticle surface, a silicon nanoparticle promotes enhancement of radiative decay by one order of the magnitude within the whole visible range. Our results can be used for other photochemical or photovoltaic processes, and strong radiative decay enhancement found for dielectric nanoantennas paves the way to radiative decays and light emitters engineering without non-radiative losses.

Tuning spontaneous radiation of chiral molecules by asymmetric chiral nanoparticles.

We have obtained analytical expressions for the radiative decay rate of the spontaneous emission of a chiral molecule located near a dielectric spherical particle with a chiral nonconcentric spherical shell made of a bi-isotropic material. Our numerical and graphical analyses show that material composition, thickness and degree of non-concentricity of the shell can influence significantly the spontaneous radiation of the chiral molecule. In particular, the radiative decay rates can differ in orders of magnitude for a chiral molecule located near the thin and thick parts of a nonconcentric shell as well as near a concentric shell made of chiral metamaterial. We also find that the radiative decay rates of the "right" and "left" chiral molecule enantiomers located near a nanoparticle with a chiral metamaterial shell can differ pronouncedly from each other. Our findings therefore suggest a way to tune the spontaneous emission of chiral molecules by varying the material composition, thickness and degree of non-concentricity of the shell in the nearby composite nanoparticle and also to enhance the chirality selection of chiral molecules in racemic mixtures.

Nonresonant surface-enhanced Raman scattering of ZnO quantum dots with Au and Ag nanoparticles.

Pronounced 10(4)-fold enhancement of Raman scattering has been obtained for ZnO nanocrystals on substrates coated with 50 nm Ag nanoparticles under nonresonant excitation with a commercial red-emitting laser. This makes feasible beyond 10(-18) mole detection of ZnO nanocrystals with a commercial setup using a 0.1 mW continuous wave laser and can be purposefully used in analytical applications where conjugated nanocrystals serve as Raman markers. For Au-coated surfaces the enhancement is much lower and the heating effects in the course of Raman experiments are pronounced.

Photoacoustic imaging of living mouse brain vasculature using hollow gold nanospheres.

Photoacoustic tomography (PAT) also referred to as optoacoustic tomography (OAT) is a hybrid imaging modality that employs nonionizing optical radiation and ultrasonic detection. Here, we describe the application of a new class of optical contrast agents based on mesoscopic hollow gold nanospheres (HAuNS) to PAT. HAuNS are approximately 40 nm in diameter with a hollow interior and consist of a thin gold wall. They display strong resonance absorption tuned to the near-infrared (NIR) range, with an absorption peak at 800 nm, whose photoacoustic efficiency is significantly greater than that of blood. Following surface conjugation with thiolated poly(ethylene glycol), the pegylated HAuNS (PEG-HAuNS) had distribution and elimination half-lives of 1.38 +/- 0.38 and 71.82 +/- 30.46 h, respectively. Compared with PAT images based on the intrinsic optical contrast in nude mice, the PAT images acquired within 2 h after intravenous administration of PEG-HAuNS showed the brain vasculature with greater clarity and detail. The image depicted brain blood vessels as small as approximately 100 mum in diameter using PEG-HAuNS as contrast agents. Preliminary results showed no acute toxicity to the liver, spleen, or kidneys in mice following a single imaging dose of PEG-HAuNS. Our results indicate that PEG-HAuNS are promising contrast agents for PAT, with high spatial resolution and enhanced sensitivity.

Acoustic signals generated by laser-irradiated metal nanoparticles.

We present a physical model that explains several sequential stages of the conversion of optical to acoustical energy when irradiating diluted suspensions of metal nanoparticles with laser pulses. Optical absorption and scattering of a single particle driven by plasmon resonance interactions in an aqueous medium are considered. Thermal effects produced by laser-irradiated nanoparticles, dynamics of vapor bubble formation, and acoustic signals from expanding bubbles formed around heated nanoparticles are calculated. Stochastic features of the pressure magnitude emitted as a result of low-fluence irradiation of suspensions are also discussed. The probabilistic distribution of pressure magnitude from individual bubbles was found to obey Zipf's law for low concentrations of nanoparticles, while increasing their concentration brings the pressure magnitude distribution into conformance with the Gaussian law.