Theoretical and experimental investigation of the near field under?ordered silica spheres on substrate

Investigation on the optical resonance and near field effects of a 2D periodic dielectric spheres on metallic surfaces by combining theoretical calculations with experimental studies were carried out. The light scattering and coupling was numerically studied. Nanostructures were fabricated on the metallic surfaces using these arrays of micro- and nano-spheres with a single laser pulse (KrF, λ=248 nm). The occurrence of such nanostructures is well explained by the theoretical calculations. The results can be useful in investigation and development of spheres-assisted nano-patterning.     

Enhanced photoelectrochemical performance of ZnO photoanode with scattering hollow cavities

Abstract ZnO nanoparticles with average diameter of 12 nm were used to fabricate ZnO photoanodes by electrohydrodynamic (EHD) technique for dye-sensitized solar cells (DSSCs). To enhance the light scattering and conversion efficiency, the ZnO film with scattering hollow cavities (HCs) was realized by calcining polystyrene spheres (PSs) in the film. The films had strong light scattering ability and the overall light to electricity conversion efficiency (η) was improved and reached 5.5% under illumination of simulated solar light (AM-1.5, 100 mW/cm²).     

Characterization of luminescent chromophore obtained from silica spheres

Blue light emitting chromophores have been separated from silica spheres by soaking them into acetone for 120 days. The luminescent chromophores were not obtained from other solvents, including ether, methanol, ethanol, 2-propanol, chloroform and tetrahydrofuran. According to the Fourier transform infrared spectrum, the luminescent material is composed of C–OH, –CH₂, –CH₃, C=O, and Si–O–Si. UV–visible absorption peak of the chromophore is at 5.17 eV (240 nm). Field emission scanning electron microscope images show small cracks on the surface of aged spheres. The luminescence peak was at 2.81 eV (441 nm) for excitation energy between 3.88 and 3.35 eV and slightly shifted toward lower energy for excitation energy lower than 3.35 eV. The deconvoluted luminescent spectrum shows two emission bands at 3.08 and 2.74 eV, which are well-matched the oxygen deficient center model. Compared to the absorption peak (5.17 eV) and the emission peak (2.81 eV), large Stokes shift (2.36 eV) is observed.     

Rotations of eigenvibration direction in anisotropic crystals

The electric field of incident light induces dipoles in anisotropic media, vibrating in two perpendicular directions of the principal axes. Because of the tensor property of the dielectric constant, an induced dipole is subject to a torque, tending to rotate it about the axis parallel to the propagation direction. The directions of eigenvibration of the ordinary (o-ray) and extraordinary (e-ray) waves are no longer perpendicular in this sense. We propose here the relationships to describe the rotation of the induced dipole in the perpendicular electric fields. The rotation angles are found to increase with increasing dielectric constants and electric field strength of the incident light, exhibiting large values near the resonance frequencies in the infrared range at the azimuth angle /4 of the polarized incident light. Piezoelectric and ferroelectric crystals have a large value of the dielectric constant in the infrared frequency range. Rotations of the vibration direction of the o-ray and the e-ray waves are shown in the infrared transmission spectra recorded by incidence of the polarized light and transmission through piezoelectric and ferroelectric crystals (-quartz, LiNbO₃, and LiTaO₃). Interference of the o-ray and the e-ray waves transmitted through the crystals confirms the rotations of the vibration directions, a self-modulation effect of light in piezoelectric and ferroelectric crystals induced by the electric field of the propagating light.     

Influence on SERS enhancement factor of the components of an artificial opal loaded with metal NPs: A systematic study

We have inquired about the influence of composite artificial opal components on its SERS enhancement factor (EF). Particularly, we considered metal (100 nm) and dielectric spheres (290 nm), and an excitation wavelength of 632 nm. We show that the electric field of a SiO₂ sphere is weaker and more uniform as its porosity increases. Additionally, a porous sphere promotes a lower EF compared to that of a non-porous sphere. The optical response of the composite opal is insensitive to the polarization state of the incident field. A SERS EF of 10⁴ is reachable with an opal loaded with Au or Ag NPs. In general, the dielectric spheres affect the SERS EF intensity of the metal NPs. From the optical spectra, we observed that with a 632 nm wavelength, the composite opal is out of resonance.     

Local crystallization in an oxyfluoride glass doped with Er3+ ions using a continuous argon laser

Local crystalline formation in erbium doped oxyfluoride glass has been obtained under a cw Argon laser irradiation up to 1.8 W pumping power. By exciting at 514 nm, the emission from 800 nm and 850 nm corresponding to the ⁴S_3/2(²H_11/2)→⁴I_13/2 electronic transitions have been analyzed both inside and outside the irradiated area. The changes in the emission spectra indicate that the high power Ar laser irradiation has resulted in a localized desvitrification process. The temperature dependence of the fluorescence intensity ratio of the 800 nm and 850 nm emission bands has been used to determine the temperature of the irradiated zone. Moreover, the average lifetime of the ⁴S_3/2(²H_11/2) thermalized levels have been measured as a function of the excitation spot position. An important decrease is observed at the irradiated area. These results confirm that a localized cristalline phase has been created by the laser action.     

Electric and magnetic losses and gains in determining the sign of refractive index

Within the framework of classic electromagnetic theories, we have studied the sign of refractive index of optical medias with the emphases on the roles of the electric and magnetic losses and gains. Starting from the Maxwell equations for an isotropic and homogeneous media, we have derived the general form of the complex refractive index and its relation with the complex electric permittivity and magnetic permeability, i.e. , in which the intrinsic electric and magnetic losses and gains are included as the imaginary parts of the complex permittivity and permeability, respectively, as  = _r + i_i and μ = μ_r + iμ_i. The electric and magnetic losses are present in all passive materials, which correspond, respectively, to the positive imaginary permittivity and permeability _i > 0 and μ_i > 0. The electric and magnetic gains are present in materials where external pumping sources enable the light to be amplified instead of attenuated, which correspond, respectively, to the negative imaginary permittivity and permeability _i < 0 and μ_i < 0. We have analyzed and determined uniquely the sign of the refractive index, for all possible combinations of the four parameters _r, μ_r, _i, and μ_i, in light of the relativistic causality. A causal solution requires that the wave impedance be positive Re{Z} > 0. We illustrate the results for all cases in tables of the sign of refractive index. One of the most important messages from the sign tables is that, apart from the well-known case where simultaneously  < 0 and μ < 0, there are other possibilities for the refractive index to be negative n < 0, for example, for _r < 0, μ_r > 0, _i > 0, and μ_i > 0, the refractive index is negative n < 0 provided μ_i/_i > μ_r/_r.     

Preparation of phosphors AEu(MoO4)2 (A?=?Li, Na, K and Ag) by?sol-gel method

A series of double molybdates phosphors AEu(MoO₄)₂ (A = Li, Na, K and Ag) have been prepared by sol-gel method. Their crystal structure and luminescent properties have also been investigated in a comparable way. The crystallization processes of the phosphor precursors were characterized by X-ray diffraction (XRD) and thermogravimetry-differential thermal analysis (TG-DTA). Field emission scanning electron microscopy (FE-SEM) was also used to characterize the shape and size distribution of the phosphors. Samples except KEu(MoO₄)₂ showed tetragonal scheelite structure in the range of our experiments, and no phase transition appeared. Phosphor KEu(MoO₄)₂ possessed two structures, and the phase transition took place at about 800°C. All samples with high purity could be obtained at about 500°C for 5 hours, and they all showed intense red light peaked at 616 nm originated from ⁵D₀→⁷F₂ emission of Eu³⁺ under the excitation of 465 nm or 394 nm light. The excitation spectra of phosphors AEu(MoO₄)₂ (A = Li, Na, and K) are composed of a strong broad charge transfer (CT) band and some sharp lines, and the relative intensity of CT band, the two strongest absorption lines at 395 nm and 465 nm are comparative, so these three phosphors are good red phosphor candidates for violet or blue LEDs. For the excitation spectrum of phosphor AgEu(MoO₄)₂, intensities of CT band and the absorption line at 395 nm are much weaker than that of line at 465 nm, thus phosphor AgEu(MoO₄)₂ is only suit for GaN-based blue LED.     

Laser-induced desorption of Na-dimers

We find that Na-dimers are desorbed in a thermal process if rough Na surfaces are irradiated with pulsed laser light of λ=532 nm. In contrast, for light of λ=355 nm, Na₂ can be detached in a non-thermal reaction at low laser fluences. This is concluded from the kinetic energy distributions of the dimers determined by time-of-flight measurements using a second laser at λ=248 nm for photoionization. The transition from non-thermal to thermal desorption at large fluences of the laser light can also be identified. Received: 23 July 1996 / Accepted: 26 August 1996     

Synthesis of a fluorinated photoresist for optical waveguide devices

A linear fluorinated bis-phenol-A novolac resin (LFAR) for optical waveguide was synthesized based on 4,4′-(hexafluoro-isopropylidene)diphenol, epoxy chloropropane and formaldehyde. Negative fluorinated photoresist (FP) was made by composing the LFAR, diphenyl iodonium salt and solvent. The film, which was made by spin-coating FP, had good UV light lithograph sensitivity, large hardness and high glass transition temperature (T _g >170°C, after crosslinking). Low-loss optical waveguides with very smooth top surface were fabricated from the resulting FP by direct UV exposure and chemical development. For waveguides without upper cladding, the propagation loss of the channel waveguides was measured to be 0.21 dB/cm at 1550 nm.     

Effect of the ceramic grain size and concentration on the dynamical mechanical and dielectric behavior of poly(vinilidene fluoride)/Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> composites

Laser-induced backside wet and dry etching (LIBWE and LIBDE) methods were developed for micromachining of transparent materials. Comparison of these techniques is helpful in understanding the etching mechanism but was not realized due to complications in setting up comparable experimental conditions. In our comparative investigations we used a solid tin film for dry and molten tin droplets for wet etching of fused-silica plates. A tin–fused-silica interface was irradiated through the sample by a KrF excimer laser beam (λ=248 nm, FWHM=25 ns); the fluence was varied between 400 and 2100 mJ/cm². A significant difference between the etch depths of the two investigated methods was not found. The slopes of the lines fitted to the measured data (sl_LIBDE=0.111 nm/mJ cm⁻², sl_LIBDE=0.127 nm/mJ cm⁻²) were almost similar. Etching thresholds for LIBDE and LIBWE were approximately 650 and 520 mJ/cm², respectively. To compare the dependence of etch rates on the pulse number, target areas were irradiated at different laser fluences and pulse numbers. With increasing pulse number a linear rise of depth was found for wet etching while for dry etching the etch depth increase was nonlinear. Secondary ion mass spectroscopic investigations proved that this can be due to the reconstruction of a new thinner tin-containing surface layer after the first pulse.     

Uniform Fe3O4–PANi/PS composite spheres with conductive and magnetic properties and their hollow spheres

Core–shell multifunctional composite spheres consisting of Fe₃O₄–polyaniline (PANi) shell and polystyrene (PS) core were fabricated using core–shell-structured sulfonated PS spheres (with uniform diameter of 250 nm) as templates. PANi was doped in situ by sulfonic acid resulting the composite spheres are well conductive. Dissolved with solvent, PS cores were removed from the core–shell composite spheres and hollow Fe₃O₄–PANi spheres were obtained. Removing the PANi and PS components by calcinations produced hollow Fe₃O₄ spheres. The cavity size of the hollow spheres was uniformly approximate to 190 nm and the shell thickness was 30 nm. The cavity size and the shell thickness can be synchronously controlled by varying the sulfonation time of the PS templates. The shell thickness in size range was of 20–86 nm when the sulfonation time was changed from 1 to 4 h. These resulting spheres could be arranged in order by self-assembly of the templates. Both the Fe₃O₄–PANi/PS composite spheres and the hollow Fe₃O₄ spheres exhibit a super-paramagnetic behavior. Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray powder scattering were used to characterize these as-prepared spheres. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Magnetic multilayers on nanosphere arrays with various curvature radius

[Co/Pt]_n multilayers with different Co thickness have been deposited on a silicon (Si) substrate to obtain better perpendicular anisotropy. The 0.5 nm thickness of the Co layer was chosen as the optimized thickness of the multilayer. Magnetic nanostructures with cap configuration were fabricated based on the template of polystyrene (PS) colloid sphere arrays with various curvature radius. Compared to the flat multilayer, the cap multilayer showed an oblique average anisotropy axis. When the curvature radius of the colloidal sphere increased, the shape of the multilayers changed from ellipsoidal to spherical, which led to a different dependence of magnetic properties on the field angles. The varying shape anisotropy, the dipole-dipole interaction between small magnetic caps, and the special nucleation mechanism on the spheres larger than 400 nm caused the M_r/M_s ratio and the coercivity to first increase and then decrease with varying curvature radius of the PS spheres.     

Radius-dependent binding or repelling forces exerted on metal nano-sphere clusters by infrared-induced plasmonic resonance

The force exerted on metal nano-particles is investigated numerically when the particles are in contact to form a cluster and are illuminated by a light of their fundamental plasmonic resonance frequency. For touching spheres, the mode of resonance changes drastically from those of separate spheres, and the resonance typically appears in the infrared wavelength range. For silver and gold two-sphere clusters, i.e. homo-dimers, of various radii, the magnitudes and the directions of the exerted forces are analyzed. It is found that the field enhancement in the gap region between the spheres depends largely on the sphere radius, and the force on the fundamental resonance exhibits binding only for small spheres; the greatest binding force is observed for radii of 40–60 nm; and the force turns to repelling when the radius becomes greater than approximately 100–150 nm as the field in the gap region becomes weaker.     

Simultaneous slow and fast light in C60 solution

Recently, many researchers have reported their work about sub- and superluminal propagation. And many experiments have demonstrated the group velocity transition between slow and fast light. In this letter, the authors reported simultaneous slow and fast light in a single light beam which could be explained by the photorefractive lens-like effect and the spatial dispersion qualitatively. In our experiment, a focused light beam at 532 nm normally incident upon a thin quartz cell full of C₆₀ solution and spatial diffraction rings were observed behind the cell. Recurring to a pinhole diaphragm, we measured the group velocity of light of different position on the diffraction rings. The experimental results demonstrated that slow and fast could exist in a single beam at the same time. We could acquire slow or fast light just by adjusting the position of the detector and keeping the experimental parameters, such as: modulation frequency and incident intensity, unchanged. Our experiment put forward a new way to control the group velocity in nonlinear optical material.     

Architectures of YF<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> solid and hollow sub-microspheres: a facile arginine-assisted hydrothermal synthesis and luminescence properties

Solid and hollow YF₃:Eu³⁺ spheres assembled by nanorods have been successfully synthesized via a facile arginine-assisted hydrothermal method and followed by a subsequent heat-treatment process. The experimental results reveal that the as-prepared YF₃:Eu³⁺ spheres are composed of the nanorods with a diameter of 20–50 nm and a length of 200–500 nm, the morphologies of YF₃:Eu³⁺ have been changed from solid to hollow spheres assembled by nanorods. With increase of hydrothermal temperature and time, the diameter of YF₃:Eu³⁺ spheres can be controlled from 300 to 800 nm. The solid and hollow spheres show an intense orange red emission peak near 595 nm, corresponding to the ⁵D₀ → ⁷F₁ transition of Eu³⁺. The possible formation mechanism for the hollow spheres has been presented in detail. This amine acid-assisted method is very simple, economic and environmental friendly for organic-free solvent, which would be potentially used in synthesizing other hollow materials.     

Femtosecond-laser nanofabrication onto silicon surface with near-field localization generated by plasmon polaritons in gold nanoparticles with oblique irradiation

Nanohole fabrication process with gold nanoparticles irradiated by femtosecond laser at different incident angles is investigated. Nanoparticles with diameter of 200 nm and laser irradiation with center wavelength of 800 nm are used in the present study. The analysis of the electromagnetic field distribution in the near-field zone of the particle is made by simulations based on finite-differential time domain (FDTD) method. It is shown that when gold nanoparticle is irradiated by laser pulse surface plasmon excitation can be induced, and associated with it, high-intensity near field is produced in a limited area around the particle. It is found that the change of the irradiation conditions by means of irradiation from various incident directions gives a possibility of laser nanoprocessing with tunable characteristics. Our results show that enhanced optical intensity is able to be induced on the substrate surface regardless of incident direction of the laser due to the image charge interaction with the substrate. Furthermore, the use of p-polarized laser irradiation at a certain angle gives a minimum of the spatial dimensions of the enhanced zone on the substrate which is about two times smaller than that obtained at normal incidence.     

Broadband four-wave optical parametric amplification in bulk isotropic media in the ultraviolet

We report on four-wave optical parametric amplification of the ultrashort ultraviolet light pulses in bulk fused silica and CaF₂. Exact phase-matching in these isotropic media is achieved by means of non-collinear interaction with cylindrical beam focusing. Four-wave optical parametric amplifier efficiently operates in the UV spectral range with 1-ps laser pulses, delivering amplified signal energy exceeding 50 μJ using millijoule pump pulses in the visible (527 nm). Results of scanning of the parametric gain profile suggest that broad amplification bandwidth as wide as ∼20 nm (at FWHM) under these experimental settings is achieved, which might support amplification of sub-10-fs ultraviolet pulses with central wavelength around 330 nm. It is also shown experimentally and verified theoretically that the parametric gain profile exposes a distinct inhomogeneity and its bandwidth notably broadens due to effects of self- and cross-phase modulation imposed by the intense pump beam.     

Sub-Doppler fluorescence on the atomic <Emphasis Type="Italic">D</Emphasis><Subscript>2</Subscript> line of a submicron rubidium-vapor layer

An extremely thin cell (ETC) with the thickness of a Rb atomic vapor layer in the range of 100–300 nm was fabricated. It is demonstrated that a simple laser-diode technique with a single resonant light beam is sufficient to observe separately all of the atomic hyperfine transitions of the D ₂ line of Rb (780 nm) and also allows us to measure the relative transition probabilities of the hyperfine transitions. The onset of collisional self-broadening of the hyperfine transitions as the number density of atoms increases was studied. The detrimental role of the atoms with slow longitudinal velocity in the sub-Doppler response of the Rb ETC is demonstrated by studies in which the cell is tilted from normal incidence of the laser beam. It is also shown that using an ETC allows us to resolve in a moderate external magnetic field the Zeeman splitting of the hyperfine transitions of the ⁸⁷Rb D ₁ transition F _g=1F _e=1,2. Received: 19 February 2003 / Revised version: 4 April 2003 / Published online: 2 June 2003 RID="*" ID="*"Corresponding author. Fax: +374/32-31172, E-mail: david@ipr.sci.am     

Method of frustrated total reflection in spectroscopy of surface polaritons in almost perfectly conducting metals

The standard technique for surface polaritons excitation by a prism coupling in Otto configuration is applied for investigation of almost perfectly conducting (pec) metals like tantalum irradiated by a collimated He-Ne laser radiation (λ ₀ = 632.8 nm). In pec metals the imaginary part of the relative dielectric permittivity (ɛ″) is quite larger than the modulus of the real part of the same quantity (ɛ′ < 0, ɛ″ ≫ | ɛ′ |). Under this condition the single Lorentz dip of the reflectivity coefficient is proven to exist and is given in an analytical form, which follows from simplification of the usual multilayer Fresnel formula. In the case of a deterministically curved metal surface an approximate solution to the reduced Rayleigh integral equation appropriate for the Otto configuration is also given. These two theoretical deductions are compared with experimental data that have been produced by us for the reflectivity into the prism region from a bulk tantalum sample.