Rare-earth ions embedded in glassy matrices are promising materials for photon upconversion processes, e.g. to convert near infrared light to frequencies above the band gap of a solar cell to make it available for electrical power generation. One strategy to optimize the efficiency of such upconversion processes is to embed the active ions in a host matrix with minimal losses to non-radiative relaxation. For the model system of trivalent neodymium in fluorochlorozirconate (FCZ) glass it has been shown recently that a uniform growth of BaCl2 nanocrystals inside such glasses can decrease the probability of multi-phonon relaxation (MPR) drastically, leading to a huge increase in upconversion intensity for monochromatic illumination. To identify the key processes which may enhance or diminish the total upconversion efficiency, a comprehensive description for the optical dynamics of neodymium in FCZ glass ceramics has been developed on the basis of a rate equation system, including ion-photon, ion-phonon, and ion-ion interactions. An effective medium approach is utilized to account for the neodymium located in BaCl2 nanocrystals or the FCZ glass bulk, respectively. The numerous parameters required to enable for a reliable numerical simulation of the processes are obtained from theoretical approaches like Judd-Ofelt theory, as well as from experimental studies of luminescence decay after femtosecond excitation at various wavelengths and luminescence spectra under cw illumination at 800 nm wavelength. This rate equation model enables for a convenient, self-consistent description of all time-resolved and cw experiments on samples with different neodymium concentration. On this basis, the power dependence of upconversion spectra can be simulated in good agreement with the experimental result for 800 nm cw illumination. The model therefore forms an excellent tool for optimizing the upconversion efficiency of rare-earth doped luminescent material also under realistic (broadband illumination) conditions.
The process of ultrashort laser-assisted selective removal of thin dielectric layers from silicon substrates has a large
potential for technological applications, the most straightforward one being an energy-efficient and environmentally
compatible method to produce contact openings on crystalline silicon solar cells. Using photon energies above the band
gap energy, ablation of such thin transparent layers is possible without noticeable damage of the silicon substrate. To
understand in detail the physics behind this damage-free delamination, experiments with a variety of laser parameters
were done, utilizing in particular wavelengths from UV to mid-infrared and pulse durations between 50 and 2000 fs.
Experiments were also conducted using different transparent materials on silicon, e.g. SiO2 and SixNy. The ablated
regions were carefully analyzed by light microscopy (LM), atomic force microscopy (AFM), Raman spectroscopy (RS),
scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron energy loss spectroscopy
(EELS). The results give evidence that the mechanism of damage-free ablation is initiated by ultrafast creation of
electron-hole plasma by the ultrashort laser pulse itself followed by non-thermal decomposition of an ultrathin Si layer of
a few nm thickness only. This process works best in the region of moderate substrate absorption, i.e. using laser photon
energies only slightly above the band gap, and for the shortest pulses. In contrast, laser energy input into the dielectric
layer by addressing either the UV absorption or a vibrational resonance (e.g. at λ = 9.26 μm for SiO2) allowed ablation
only in connection with partial damage of the substrate.
Transparent dielectric layers on semiconductors are used as anti-reflection coatings both for photovoltaic applications
and for mid-infrared optical elements. We have shown recently that selective ablation of such layers is possible using
ultrashort laser pulses at wavelengths being absorbed by the semiconductor. To get a deeper understanding of the
ablation mechanism, we have done ablation experiments for different transparent materials, in particular SiO2 and SixNy
on silicon, using a broad range of wavelengths ranging from UV to IR, and pulse durations between 50 and 2000 fs. The
characterization of the ablated regions was done by light microscopy and atomic force microscopy (AFM). Utilizing
laser wavelengths above the silicon band gap, selective ablation of the dielectric layer without noticeable damage of the
opened silicon surface is possible. In contrast, ultrashort pulses (1-2 ps) at mid-infrared wavelengths already cause
damage in the silicon at lower intensities than in the dielectric layer, even when a vibrational resonance (e.g. at λ = 9.26
μm for SiO2) is addressed. The physical processes behind this, on the first glance counterintuitive, observation will be
discussed.
We explore different approaches to achieve co-doping of glasses with rare earth ions and metallic nanoparticles, and to
manipulate the spectral position of the particles' surface plasmon resonance. The final goal is to find a composite
material with improved efficiency of frequency up-conversion of light for photovoltaic applications. The potential for
improvement has been shown by theoretical calculations predicting that absorption and emission probabilities of the ions
can be enhanced when the plasmon resonance of the nanoparticles is close to the respective transition frequency of the
ions. In this work we demonstrate the sequential co-doping of glasses already containing rare-earth ions with Ag
nanoparticles, as well as implantation of rare-earth ions in glasses which already contained metallic nanoparticles. It
could also be demonstrated that the surface plasmon resonance of the created particles can be tuned by femtosecond
laser induced shape transformation of the Ag clusters.
The shapes of initially spherical Ag nanoparticles in glass were permanently changed by fs laser irradiation. This shape
transformation of the nanoparticles results in an optical dichroism of the material, strongly depending on the actual
irradiation parameters such as intensity, number of pulses per irradiated spot and laser wavelength. The proposed
technique allows modifying the optical properties of glass containing metallic nanoparticles and can be used for the
production of dichroic or polarizing microstructures in the visible and near infrared region with high polarization
contrast.
Irradiation of spherical silver nanoparticles in glass by
linearly-polarized intense femtosecond laser pulses close to the surface plasmon resonance results in irreversible shape transformations. In this context, the spectral positions of
plasmon resonances as a function of particle size and basic shapes are well-understood theoretically and experimentally; however, the dynamical information regarding the laser-induced shape transformation mechanisms is still a matter of interest. To investigate these dynamics we introduce a single-color double-pulse experiment, where the sample is irradiated by two time-delayed pulses of equal intensity. Different nanoparticle shape elongations can be produced depending on the delay between two irradiating pulses. Analyzing the resultant shifts of absorption bands for each delay
gives valuable information on the evolution of nanoparticle shape changes. Possible shape modifying mechanisms including nanoparticle ionization, extreme lattice heating and excess energy transfer from the hot nanoparticle to the glass matrix are observed and discussed.
A simple technique to prepare large-area, regular microstructures in glass containing silver nanoparticles is presented. Here the modification of spatial distribution of the nanoparticles is achieved using a direct current (DC) electric field at moderately elevated temperatures. The technique exploits the recently reported effect of "electric field-assisted dissolution" (EFAD) of silver nanoparticles during which the silver nanoparticles embedded in a glass matrix can be destroyed and dissolved in the glass in form of Ag+ ions by a combination of an intense DC electric field (~1kV) and moderately elevated temperature (~280°C). This process can lead to a total transparency of the nanocomposite glasses, which to our knowledge can not be achieved via any other technique.
In this work, the possibility to produce orderly-oriented array of embedded, 2-D, micron size optical structures in silver-doped nanocomposite glass is demonstrated. This could lead to an easy way for production of many useful optical devices based on the composite materials.
By irradiating glass containing spherical Ag nanoparticles successively with fs laser pulses at different wavelengths, we were able to produce three-dimensional, permanent anisotropic modifications based on shape deformations of the nanoparticles in this nanocomposite material. This novel method is able to create dichroism in the visible and near IR part of the spectrum by deformation of nanoparticles to oblong shapes oriented parallel to the laser polarization. Using samples with a vertical gradient of the fill factor of Ag nanoparticles in the glass substrate and an accordingly inhomogeneous broadening of the surface plasmon band, modifications in various depths can be made using different excitation wavelengths. The induced modifications are reversible: heating to ≈ 600oC restores the spherical shape of Ag nanoparticles. This technique can be useful for manufacturing of different, 3D, polarization and wavelength selective micro-devices such as polarizers, filters, gratings, display and rewriting optical 3D data storage devices. As examples, we will demonstrate in this paper how (i) three areas of different color can be produced in three different depths of the sample and (ii) how a series of multicolor irradiations can be used to produce dichroic structures of high polarization
contrast.
Glass containing spherical silver nanoparticles shows a strong extinction band in the visible range due to the surface plasmon resonance (SPR) of the particles. Irradiating this material with intense, ultrashort laser pulses with a wavelength close to the SPR leads to permanent changes of its optical properties. In particular, using linearly polarized pulses, we observed strong dichroism; the latter is nanoscopically caused by deformation of the particles to ellipsoidal shapes with an additional halo of small silver particles around the central one, with a preferential orientation. In case of a single laser shot of sufficient intensity this orientation is orthogonal to the laser polarization, whereas multi-shot irradiation usually causes preferential orientation along the laser polarization. This effect is quite useful for the production of dichroitic or polarizing microstructures, and optical elements or optoelectronic devices. In this paper we describe the results of a variety of experimental studies (mostly femtosecond laser pump-probe, electron microscopy, photoluminescence) on the understanding of the physical processes, which show clearly that ultrafast ejection of electron and silver ions into the glass matrix is the starting mechanism, whereas in the course of deformation diffusion processes controlled by the local temperature play a decisive role for the final particle shapes (and thus the optical properties after laser treatment).
We study different effective medium theories for describing the optical behaviour of composites consisting of spherical metallic inclusions embedded in a dielectric matrix. The analysis is performed according to the Bergman spectral density theory. This theory establishes that any effective medium model has an integral representation in terms of a function (the spectral density) that depends on the geometry of the two-phase mixture and is independent of the optical constants of the composing materials. We review classical effective medium theories (Maxwell-Garnett and Bruggeman models) according to their spectral density. Furthermore, numerical simulations based in recent works allow studying the influence of different geometric parameters in the spectral density and compare the results with the classical theories.
Highly-ordered two dimensional arrays of monodisperse silver and nickel nanowires were prepared in an alumina matrix. The nearly 100% filling of the template with metal was obtained by improved electrochemical deposition technique. The light propagation in the direction of the long axis of the metal nanowires were studied by far field spectroscopy and the results were compared with the generalized Mie theory. By selectively dissolving the matrix at a constant etching rate the we investigate the surface enhanced Raman scattering (SERS) and the results are interpreted with theoretical models. The enhanced SERS signal can be recorded until the whole matrix was removed and the ordering of the metal nanowires collapses.
Access to the requested content is limited to institutions that have purchased or subscribe to SPIE eBooks.
You are receiving this notice because your organization may not have SPIE eBooks access.*
*Shibboleth/Open Athens users─please
sign in
to access your institution's subscriptions.
To obtain this item, you may purchase the complete book in print or electronic format on
SPIE.org.
INSTITUTIONAL Select your institution to access the SPIE Digital Library.
PERSONAL Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.