Laser-assisted growth of gold nanoparticles: Shaping and optical characterization

We demonstrate that supported gold nanoparticles with a given well-defined shape can be produced by laser-assisted growth. For this purpose, gold nanoparticles with average radii ranging from 1.5 to 13 nm, i.e., coverage between 0.45 × 10¹⁶ and 5.6 × 10¹⁶ atoms/cm², were prepared at room temperature by self-assembly of atoms deposited on quartz and sapphire substrates. For analysis of the samples, the optical spectra of the particles were measured with p-polarized light and photon energies in the range of 1.3 to 3.1 eV. Irradiating the particles during growth with laser light of different wavelengths to stimulate surface plasmon excitation made it possible to stabilize mean axial ratios between 0.19 and 0.98. The influence of the laser fluence on the shape of the nanoparticles was also investigated and shows that the position of the surface plasmon resonance shifts to higher energies as the fluence rises. Optimum growth conditions to shape gold nanoparticles with axial ratios close to unity (spheres) with a relatively low laser fluence of 60 ± 5 mJ/cm² have also been found. The results of our experiments show that laser-assisted growth is a powerfultechnique to control the shape of nanoparticles.     

Tunable coupled plasmon modes via nanoshell particle chains

Coupled plasmon modes have been studied theoretically in periodic chains of nanoshell particles embedded in a graded dielectric host. These chains not only sustain a variety of localized modes as unshelled nanoparticle chains, but also offer precise control of the localization-delocalization transition among these modes by varying the permittivity contrast and/or core-shell radius ratio. By optimizing these parameters, the upper band can be tuned into higher frequencies while the lower band can be tuned into the optical communication frequencies for practical application. We also discuss the Ohmic loss effects in the metallic component of the nanoshells.     

Challenge of ultra high frequency limit of permeability for magnetic nanoparticle assembly with organic polymer—Application of superparamagnetism

Permeability and its upper limitation frequency of superparamagnetic nanoparticle type magneto-dielectric hybrid material were theoretically and experimentally investigated. The Landau-Lifschitz-Gilbert equation without any interaction between nanoparticles revealed that the blocking resonance frequency was able to exceed the ferromagnetic resonance frequency originating from the intrinsic magnetocrystalline anisotropy field by decreasing particle size, resulting in ultra fast switching of superparamagnetic moment in GHz range. In the case of Fe nanoparticles, the blocking resonance frequency can be increased to 130 GHz by reducing particle size to 1 nm. The experiment results for Fe₃O₄ and Fe nanoparticle assemblies supported the validity of our calculation results. Thus, superparamagnetic nanoparticle assembly could be promising material for high frequency use over 10 GHz range.     

Blue luminescent silicon nanocrystals prepared by short pulsed laser ablation in liquid media

The pulsed laser processing in liquid media is an attractive alternative to produce room temperature luminescent silicon nanocrystals (Si-ncs). We report on a blue luminescent Si-ncs preparation by using nanosecond pulsed laser (Nd:YAG, KrF excimer) processing in transparent polymer and water. The Si-ncs fabrication is assured by ablation of crystalline silicon target immersed in liquids. During the processing and following aging in liquids, oxide based liquid media, induce shell formation around fresh nanocrystals that provides a natural and stable form of surface passivation. The stable room temperature blue-photoluminescent Si-ncs are prepared with maxima located around ∼440 nm with corresponding optical band gap around ∼2.8 eV (∼430 nm). Due to the reduction of surface defects, the Si-ncs preparation in water, leads to a narrowing of full-width-half-maxima of the photoluminescence spectra.     

Tailor-made metal nanoparticles as SERS substrates

In this contribution we summarize recent experiments with the objective to generate optimized substrates for surface-enhanced Raman spectroscopy (SERS). For this purpose, the well-established laser-assisted growth technique has been applied, which relies on a precise control of the growth kinetics of supported metal nanoparticles. With this method reproducible and stable SERS substrates with tailor-made optical properties possing best field enhancements were produced for specific excitation wavelengths and detection ranges. Optimization of the SERS substrates has been achieved by stabilizing the localized surface plasmon polariton resonance (SPR) of gold nanoparticles in the vicinity of the laser wavelength of λ=647 nm and λ=785 nm used for SERS excitation. After nanoparticle preparation, SERS spectra of pyrene were obtained using naturally grown nanoparticles and nanoparticles prepared by laser-assisted growth. The most important result is that the optimized substrates prepared by laser-assisted growth exhibit a significantly higher signal-to-noise ratio as compared to naturally grown nanoparticles. They are even better than substrates whose SPR has been tuned to the excitation wavelength by an elevated temperature during preparation. Another important observation is that all SERS spectra exhibit excellent reproducibility and the substrates do not show degradation during the measurements. Finally, the SERS enhancement factors due to the optimized substrates have been estimated and are on the order of 10⁵ to 10⁶.     

Small angle neutron scattering study of disordered and crystalline iron nanoparticle assemblies

Monodisperse surfactant-coated iron nanoparticles are used to form both disordered nanoparticle assemblies and ordered face-centered cubic nanoparticle crystals. The structural order is probed by small angle X-ray scattering, and the magnetic scattering is studied using small angle neutron scattering. The magnetic scattering corresponding to different length scales is interpreted in terms of collective correlations among the particles within the assemblies.     

Optical properties and ultrafast electron dynamics in gold–silver alloy and core–shell nanoparticles

Silver and gold are the two most popular metals used for many nanoparticle applications, such as surface enhanced Raman scattering or surface enhanced fluorescence, in which the local field enhancement associated with the excitation of the localized surface-plasmon–polariton resonance (SPR) is exploited. Therefore, tunability of the SPR over a wide energy range is required. For this purpose we have investigated core–shell nanoparticles composed of gold and silver with different shell thicknesses as well as the impact of alloying on these nanoparticles due to a tempering process. The nanoparticles were prepared by subsequent deposition of Au and Ag atoms or vice versa on quartz substrates followed by diffusion and nucleation. Their linear extinction spectra were measured as a function of shell thickness and annealing temperature. It turned out that different gold shell thicknesses on silver cores allow a tuning of the SPR position from 2.79 to 2.05 eV, but interestingly without a significant change on the extinction amplitude. Heating of core–shell nanoparticles up to only 540 K leads to the formation of alloy nanoparticles, accompanied by a back shift of the SPR to 2.60 eV. Calculations performed in quasi-static approximation describe the experimental results quite well and prove the structural assignments of the samples. In additional experiments, we applied the well-established persistent spectral hole burning technique to the alloy nanoparticles in order to determine the ultrafast dephasing time T ₂. We obtained a dephasing time of T ₂=(8.1±1.6) fs, in good agreement with the dephasing time of T _2,∞=8.9 fs, which is already included in the dielectric function of the bulk.     

A simple GUI for modeling the optical properties of single metal nanoparticles

We present a graphical user interface, based on the modified long-wavelength approximation, to compute the optical properties of single metal nanoparticles of ellipsoidal geometry (spheres, rods, and disks). The user-friendly interface allows one to readily gauge the accuracy of results obtained using the modified long-wavelength approximation. For spherical particles, up to 10-nm diameter, we confirm that our approach yields an exact correspondence with Mie theory, and gives an approximation error of less than 15% for gold (silver) particles with diameters approaching 40 nm (26 nm). Results are shown to be sensitive to the source data for the optical constants for a given material. The modular nature of the simulation platform provides a quick and intuitive guide for optical characterization experiments.     

Phase sensitive spectroscopy of the polariton modes in a ZnSe-ZnSxSe1−x heterostructure

Applying the method of spectral interferometry we investigate the phase of reflected light at a ZnSe-ZnS_xSe_1−x heterostructure. We find a series of polariton modes propagating through the ZnSe layer. They can be related to the different polariton branches split of at the heavy- and light-hole excitons. The phase shows pronounced changes around these modes. The strongest changes by 2π appear at the modes of lowest order located weakly above the exciton resonances, while they are smaller for higher modes. Our experimental findings can be explained considering spatial dispersion, Pekar's additional boundary conditions and a weak extension of the excitonic polarization into the ZnS_xSe_1−x cladding layers.     

Nonlinear optical properties of periodic gold nanoparticle arrays

Periodic Au nanoparticle arrays were fabricated on silica substrates using nanosphere lithography. The identical single-layer masks were prepared by self-assembly of polystyrene nanospheres with radius R = 350 nm. The structural characterization of nanosphere masks and periodic particle arrays was investigated by atomic force microscopy. The nonlinear optical properties of the Au nanoparticle arrays were determined using a single beam z-scan method at a wavelength of 532 nm with laser duration of 55 ps. The results show that periodic Au nanoparticle arrays exhibit a fast third-order nonlinear optical response with the nonlinear refractive index and nonlinear absorption coefficient being n₂ = 6.09 × 10⁻⁶ cm²/kW and β = −1.87 × 10⁻⁶ m/W, respectively.     

Nonlinear optical properties of Au/ZnO nanoparticle arrays

The triangular-shaped Au/ZnO nanoparticle arrays were fabricated on fused quartz substrate using nanosphere lithography. The structural characterization of the Au/ZnO nanoparticle arrays was investigated by atomic force microscopy. The absorption peak due to the surface plasmon resonance of Au particles at the wavelength of about 570 nm was observed. The nonlinear optical properties of the nanoparticle arrays were measured using the z-scan method at a wavelength of 532 nm with pulse duration of 10 ns. The real and imaginary part of third-order nonlinear optical susceptibility, Re χ⁽³⁾ and Im χ⁽³⁾, were determined to be 1.15 × 10⁻⁶ and −5.36 × 10⁻⁷ esu, respectively. The results show that the Au/ZnO nanoparticle arrays have great potential for future optical devices.     

Three-dimensional analysis of silver nano-particles doping effects on super resolution near-field structure

The super resolution near-field structure which incorporates a AgOx thin film was studied through the calculation using three-dimensional (3D) finite-difference time-domain method. The influences of the optical field distribution generate by some factors, e.g., the polarization direction, the wavelength of incident light and the size of silver nano-particles, which are sensitive to the surface plasmon resonance are discussed in detail. The goal of this study is to explain the physical mechanisms responsible for the super-resolution near-field structure phenomena in 3D model and give a better understanding of the optical properties between AgOx layer and incident light.     

Decay dynamics of ultraviolet photoluminescence in ZnO nanocrystals

Time resolved photoluminescence (PL) measurements at low temperature are performed on colloidal ZnO nanocrystals dispersed in t-butanol. Considering the particle size dependence of the decay times we conclude that the luminescence is composed of two trap related emissions one of which undergoes lifetime shortening due to a non-radiative process. Initial fast shift of the spectrum within 30 ps is observed and it is interpreted as a fast hole cooling just after the excitation.     

The plasmon and distribution effects between incident light and active layer in PtOx-type super-resolution near-field structure

The plasmon and distribution effects of collective localized surface plasmons between incident light and active layer of PtO_x-type super resolution near-field structure (super-RENS) have been studied using finite-difference time-domain method. Four types of distribution of Pt nanoparticles, i.e., type A, B, C, and D in active layer are investigated. We find that type C and D in active layer can provide higher field intensity in a wider range of particle size when the particle sizes are varied, and the out-going filed emerging from the active layer exhibit smaller spot size than those of type A and B. Type B, C and D also provide the additional path longer than that of type A, and excite more evanescent field which located in the far edge of the bubble from the optical axis of the incident beam. Results show that the type C structure is the best choice in the view point of designing the PtO_x-type super-RENS. This study provides new information to design a super-RENS with superior resolution as well as other applications in nano photonic devices.     

Optical and nonlinear optical properties of copper nanocomposite glasses annealed near the glass softening temperature

Copper nanocomposite glasses have been prepared by the ion-exchange method, and annealed at different temperatures up to and above the glass softening temperature. The absorption spectra, fluorescence spectra, and nonlinear optical transmission of the samples at 532 nm for nanosecond laser pulses, have been investigated. The optical and nonlinear optical properties of the glasses are found to be distinctly different below and above the glass softening temperature. For instance, thermal annealing up to the glass softening temperature makes the samples behave like saturable absorbers, while annealing at higher temperatures makes them behave like optical limiters. Such flexibility in controlling the optical nonlinearity in these materials makes them potential candidates for photonic applications.     

Large enhancement of Faraday rotation by localized surface plasmon resonance in Au nanoparticles embedded in Bi:YIG film

A large enhancement of the Faraday rotation, which is associated with localized surface plasmon resonance (LSPR), was obtained in a sample with Au nanoparticles embedded in a Bi-substituted yttrium iron garnet (Bi:YIG) film. On a quartz substrate, Au nanoparticles were formed by heating an Au thin film, and a Bi:YIG film was then deposited on them. A sample containing the Au nanoparticles produced by 1000 °C heating showed a resonant attenuation with narrower bandwidth in the transmission spectrum than nanoparticles of other samples formed by low-temperature heating. The sharp resonant Faraday rotation angle was 4.4 times larger than the estimated intrinsic Bi:YIG film at the LSPR wavelength; the angular difference was 0.14°. A discrepancy in the bandwidth between the transmission attenuation and the resonant Faraday rotation is discussed.     

Morphology and structure of gold-lithium niobate thin film: A laboratory source X-ray scattering study

Laboratory source X-ray scattering set-up has been used to determine the complete morphology and structure of an optically important composite thin film. Analysis of grazing incidence small angle X-ray scattering, X-ray reflectivity and powder diffraction data of Au/LiNbO₃ thin film prepared by sequential deposition of gold and lithium niobate on float glass substrate suggest that the Au-nanocrystallites are dispersed in amorphous medium, which although have average separation but do not have any long range periodicity other than growth or z-direction. The morphology of the nanocomposite thin film determined through X-ray scattering measurements agrees well with the measured optical absorption.     

Size-dependent photo-induced shift of the first exciton band in CdTe quantum dots in glass prepared by a two-stage heat-treatment process

CdTe nanocrystals were grown from commercially available RG850 Schott filter glass by two-step heat-treatment process which almost doubles the particle to matrix volume fraction. A calculation shows that a quantized-state effective mass model in the strong confinement regime might be used to deduce the average radius for the nanocrystals larger than 2 nm in radius from the energetic position of the first exciton peak in optical absorption spectrum. Size-induced shift of ∼360 meV in the first exciton peak position was observed. The steady state photoluminescence spectra exhibit a broad band red shifted relative to the first exciton band, which indicates the existence of shallow trap states. The non-linear optical properties of CdTe nanocrystals were studied by room temperature resonant photoabsorption spectroscopy. The differential absorption spectra had three-lobed structure whose size-dependent evolution was explained by bleaching of the absorption, red shift and broadening in the Gaussian absorption band used to fit the first exciton peak. A maximum red shift of 2.32 meV for the average nanocrystal radius of 4.65 nm was estimated by fitting the photomodulation spectra with a combination of first and second derivative Gaussian absorption bands. We presume that the red shift is induced by the electric field of trapped charges in surface states. Internal electric field strengths of 23 and 65 kV/cm were predicted for the average nanocrystal radii of 3.95 and 4.65 nm, respectively, with the help of second-order perturbation theory in the strong confinement limit.     

Optical properties of graded colloidal nanocrystallines with tunable structure

We propose a class of graded colloidal crystalline materials which consist of polydisperse metallodielectric nanoshells stacked in layers. We take the Lekner-Lishchuk summation method to treat the graded systems which are not tractable by conventional approach such as Ewald-Kornfeld methods. It is demonstrated that this kind of graded materials exhibit a series of sharp peaks, which merge in a broadened resonant absorption band in the optical region, in contrast to colloidal crystal containing monodisperse nanoshells or nanoparticles. Effects of various gradient profiles of the ratio of the inner/outer radii in the nanoshells and lattice geometries on the optical properties are discussed. These materials are not hard to fabricate by contemporary nanofabrication techniques and they shall be useful in the engineering of optical nanomaterials.     

Optical response of small-diameter semiconducting carbon nanotubes under exciton-surface-plasmon coupling

We analyze the optical response of small-diameter (?1 nm) semiconducting carbon nanotubes under the exciton-surface-plasmon coupling. Calculated optical absorption lineshapes exhibit the significant line (Rabi) splitting ∼0.1-0.3 eV as the exciton energy is tuned to the nearest interband surface plasmon resonance of the nanotube so that the mixed strongly coupled surface plasmon-exciton excitations are formed. We discuss possible ways to bring the exciton in resonance with the surface plasmon. The exciton-plasmon Rabi splitting effect we predict here for an individual carbon nanotube is close in its magnitude to that previously reported for hybrid plasmonic nanostructures artificially fabricated of organic semiconductors deposited on metallic films. We believe this effect may be used for the development of carbon nanotube based tunable optoelectronic device applications in areas such as nanophotonics and cavity quantum electrodynamics.