The use of lasers as the driving force of information processing for future photonic technologies is almost inevitable. As a direct consequence of this the protecting of targets from high intensity stray optical beams, the most important being the eye, via optical limiting (high suppression of high intensity optical beams whilst allowing high transmission of ambient light) is a task of immediate importance. This contribution will discuss the application of metallo-phthalocyanine compounds doped into organic polymers to produce composite films to act as passive solid-state optical limiters. A range of phthalocyanines with different metals such as zinc, indium and vanadium substituted into the central cavity doped into the comercially available polymer poly(methyl)-methacrylate, PMMA, is investigated. The nonlinear responses exhibited by the systems are modelled and fitted using a three level orbital model to quantify the nonlinear activity in an effort to elucidate certain molecular design rules for the optical limiting application of the solid-state polymer-phthalocyanine composite. In addition to this the nature and physical properties of the films that are processed are also discussed.
The change in morphology of a polymer matrix upon the introduction of carbon nanotubes is characterized in this study. Multi-walled carbon nanotubes were dispersed in the conjugated copolymer poly(m-phenylenevinylene-co-2,5-dioctyloxy-p-phenylenevinylene) (PmPV) to produce a composite material. Photoluminescence (PL) measurements show a reduction in PL efficiency as the nanotube content is increased. Electron microscopy studies have shown an ordering of the polymer around the nanotubes allowing a layer thickness of 25nm to be estimated. This observed thickness agrees well with the expected value of 55nm calculated using a model relating the PL decrease to the changes in conformation that result from polymer - nanotube interactions. Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR) techniques have been employed to investigate how the polycrystallinity of the polymer is affected due to the presence of nanotubes. The results indicate an increase in polymer crystallinity occurs due to an interfacial interaction between the polymer and the nanotube.
We have fabricated two conjugated organic polymer-multiwalled carbon nanotube (MWNT) composites and measured the MWNT content of these two hosts using electron paramagnetic resonance (EPR). These polymers were poly(m-phenylenevinylene-co-2,5-dioctyloxy-p-phenylenevinylene) (PmPV) and poly(9,9-di-n-octylfluorenyl-2,7'-diyl) (PFO). These polymers both disperse MWNTs efficiently but differ in that PFO also suspends graphitic nanoparticles. The fraction of available MWNTs suspended in PmPV rises with increasing polymer mass before saturating at approximately 50% by mass for an optimum soot to polymer mass ratio of 1:4. The optimum settling time for PFO composites was 96 hrs after which 35% of available MWNTs remained suspended. Finally the host polymers were removed by Buchner filtration and the remaining residues were investigated with transmission electron microscopy (TEM). PFO also suspends graphitic nanoparticles with a maximum diameter of approximately 100 nm, which can be attributed to the structure of the polymer itself.
Silver nanowires with different diameters are prepared within the pores of nanoporous alumina membranes. The linear optical properties of these composites are investigated (UV-Vis spectroscopy) as well as the nonlinear optical properties (Z-Scan technique). The dependence of both linear and the nonlinear optical properties on the average diameter of the silver wires is analysed, indicating that the spectral position of the plasmon resonance is red-shifted when the wire diameter is increased. This in turn leads to a different nonlinear optical behaviour. At comparatively low incident laser pulse energies all samples show saturable absorption (enhanced transmission). For higher energies, however, a second effect occurs which finally leads to an increase in the absorption coefficient. This second effect can probably be attributed to the ionisation of the silver wires due to multiphoton absorptions and a subsequent trapping of the electrons in the dielectric membrane. The ionised species, however, shows a different optical behaviour. The occurrence of this ionisation depends on the wire diameter. The larger the diameter the lower the incident laser pulse energy needed to ionise the wires. This corresponds to an increase in the linear absorption coefficient with increasing wire diameter.
Experimental measurements of nonlinear optical extinction of nanosecond laser pulses by a set of conjugated co-polymer/multi walled carbon nanotube composites dispersed in solution is reported here. The polymer poly(meta-phenylenevinylene-co-2,5-dioctyloxy-para-phenylenevinylene) and multi walled carbon nanotube composites were varied according to nanotube mass content. The fabrication technique employed to produce the composite material is discussed. The experiments were performed using an open aperture Z-scan with 6 ns gaussian pulses at 532 nm from a frequency doubled, Q-switched Nd:Yag laser. The nonlinear optical extinction of the incident pulses displays enhanced dissipation of the incident light for lower incident intensities relative to increasing multi walled carbon nanotube content. Either the multi walled carbon nanotubes or the polymer dominates the nonlinear response of the composite depending on the relative mass of polymer to nanotube. Mechanistic implications of the optical dissipation are also discussed and investigated via angular dependent scattering measurements.
Experimental measurements of optical limiting of nanosecond laser pulses by two distinctly different polymer and carbon nanostructure composite materials dispersed in solution is reported here. The polymer poly(para-phenylenevinylene-co-2,5-dioctyloxy-meta-phenylenevinylene) was used to form exclusive multi walled carbon nanotube and polymer composites. The polymer poly(9,9-di-n-octylfluorenyl-2,7-diyl) was used to form composites consisting of multi walled carbon nanotubes, other clearly defined carbon nanoparticles and polymer. The fabrication technique and material characterization steps are described, where it was found that the carbon nanostructures were stably dispersed in the polymer matrix in both cases. A range of each of these composites was prepared and varied according to carbon nanostructure mass content. The optical limiting experiments were performed using an open aperture Z-scan apparatus with 6 ns gaussian pulses at 532 nm from a frequency doubled Q-switched Nd:Yag laser. In the poly(para-phenylenevinylene-co-2,5-dioctyloxy-meta-phenylenevinylene) and exclusive multi walled carbon nanotube composite either the multi walled carbon nanotubes or the polymer dominates the nonlinear response depending on the relative mass of polymer to nanotube. In the other material saturation of the optical limiting was reached at carbon nanostructure mass percentages in excess of 3.8%, relative to the polymer mass, while the polymer exhibited no response of its own. Furthermore, the scattering of high intensity light from the materials was qualitatively probed and its angular dependence investigated. The nature of the carbon nanostructure inclusions in each material was found to significantly influence the scattering response of the composites.
Zinc-2, 9,16,23 -tetra- tert-butyl-29H, 31H -phthalocyanines and Zinc-2, 9,16,23-tetrakis-(phenylthio)-29H, 31H-phthalocyanines were recrystallized from an acetone solution to give regular shaped spherical particles of 50nm diameter, confirmed by transmission electron microscopy (TEM) and atomic force microscopy (AFM). A peak broadening of the Q-Band and a shift of the B-Band in the UV-Visible absorption spectrum combined with a significant fluorescence quenching was observed. The z-scan technique was used to investigate the non-linear optical properties and an increase of approximately 200% in the ratio of excited to ground state absorption cross sections in the crystal state was observed indicative of a significant increase in the optical limiting response of the crystals compared to the monomers.
Experimental measurements of optical limiting resulting from reverse saturable absorption in metallo-phthalocyanine and metallo-naphthalocyanine compounds are reported. Open aperture ns z-scan with Gaussian pulses are employed to investigate the interaction of high intensity light with the novel compounds. Rate equations are used to analytically solve the static state solution that simulates the excited state dynamics resulting from the nonlinear excited state absorption, and this is fitted to the experimental data. General molecular engineering trends relating the optical limiting performance of these compounds to their structural characteristics are explored and discussed.
A nonlinear optical study in poly (arylene ethynylene)(PAE) and poly (arylene vinylene) (PAV) copolymers for optical switching is presented. The principle aim of this work is to establish the polymer properties, which can be exploited in the design of materials useful for optical switching. A systematic study of the polymer parameters in solution and solid state are analysed in view of their performance as nonlinear materials. Insight is gained into the material performance, which is then related back to the structure. Wavelength dependent values of the third order nonlinear absorption coefficient (beta) and the third order nonlinear refraction coefficient (eta) 2, for all four polymers are measured using the Z-scan technique. Suitability for optical switching applications is ascertained from the linear and nonlinear absorption. Two figures of merit are presented, enabling the suitability of the materials for optical switching to be ascertained, in the wavelength region spanning 465nm through 685nm. Molecular mechanical modeling is employed to provide a preliminary view of the polymer structure to aid the understanding of the nonlinear optical and film forming properties of the polymers. Correlations are drawn between the PAE and PAV polymers, enabling the possible synthesis of the ideal material for optical switching devices at visible and near infra red wavelengths, utilizing solid state organic materials.
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.