Stilbazolium derivatives are very attractive nonlinear optical (NLO) materials for photonics and biophotonics applications due to their low linear absorption at low incident intensities in most of the visible spectral range and potentially very strong nonlinear absorption at high intensities. In this work, we investigated the nonlinear absorption of five stilbazolium derivatives, trans-4-[2-(pyrryl)vinyl]-1-methylpyridinium iodide (PVPI), trans-4-[2-(1-ferrocenyl)vinyl]-1-methylpyridinium iodide (FcVPI), trans-4-[2-(1-ferrocenyl)styryl]-1-methylpyridinium iodide (FcSPI), trans-4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide (DASPI) and trans-4-(4-aminostyryl)-1-methylpyridinium iodide (ASPI) using 6 ns and 40 ps laser pulses at 532 nm. These compounds exhibit different nonlinear absorption behavior for nanosecond and picosecond laser pulses. In the nanosecond time regime, they all show reverse saturable absorption, with PVPI exhibiting the best result. With 90% linear transmission in a 2-mm cell, the transmittance of a chloroform solution of PVPI drops to 5% when the incident fluence is increased to 7 J/cm2. The nonlinear absorption behavior of these compounds is influenced dramatically by the nature of the electron donating group, with reverse saturable absorption decreasing in the order of PVPI>FcVPI>FcSPI>ASPI>DASPI. In contrast, for picosecond laser pulses, only PVPI exhibit slight reverse saturable absorption, while DASPI, FcVPI and FcSPI show saturable absorption, and ASPI shows no nonlinear absorption. The different nonlinear absorption for ns and ps laser pulses may be due to the relative contributions from triplet excited state absorption and singlet excited state absorption.
Stilbazolium-like dyes, which contain different heterocyclic groups as electron donors and an N-methylpyridinium iodide group as an electron acceptor, are very interesting optical limiting materials. These materials exhibit low linear absorption, but potentially very strong nonlinear absorption at high intensities. In this paper, the results from investigations of the third-order susceptibilities and nonlinear refractive indices of a stilbazolium-like dye, trans-4-[2-(pyrryl)vinyl]-1-methylpyridinium iodide (PVPI), in different solvents using degenerate four wave mixing (DFWM) and Z-scan techniques with 6.8 ns laser pulses at 532 nm are reported. The molecular second-order hyperpolarizability of PVPI increases from 1.6x10-31 esu in methanol to 3.4x10-29 esu in chloroform, a factor of 212. The third-order nonlinearity of this compound is dominated by nonlinear absorption, which leads to strong optical limiting of nanosecond laser pulses. The strength of the optical limiting is dramatically influenced by the solvent used, with limiting decreasing in the order chloroform>dichloromethane, 1,2- dichloroethane>methanol, acetonitrile. While both nonlinear absorption and nonlinear scattering contribute to the optical limiting, nonlinear absorption is the dominant mechanism.
The third-order nonlinear optical properties of a methyl substituted Texaphyrin, [(CH3-TXP)Cd]Cl, were studied by degenerate four wave mixing and Z-scan techniques using 40 ps laser pulses at 532 nm. The molecular second- order hyperpolarizability ((gamma) ), the excited-state absorption cross section ((sigma) ex), the nonlinear refractive cross section ((sigma) t), and the optical limiting performances at both nanosecond and picosecond time scales have been determined. We have also studied the third- order nonlinearity of SiNc, one of the most promising optical limiting materials in literature, for comparison. The (gamma) value for [(CH3-TXP)Cd]Cl is 6.9 X 10-31 esu, which is 4 times as larger as that of SiNc. The nonlinearity of [(CH3-TXP)Cd]Cl is predominantly electronic in origin with picosecond laser pulses. The excited-state absorption cross section ((sigma) ex) and the nonlinear refractive cross section ((sigma) t) obtained from the theoretical simulation and calculation of Z-scan results are 7.0 X 10-17 cm2 and 1.7 X 10-17 cm2, respectively. The complex shows strong optical limiting performance via reverse saturable absorption for 5 ns laser pulses. The nonlinear absorption of this molecule for 40 ps laser pulses exhibits a transition from reverse saturable absorption to saturable absorption when the fluence is higher than 0.3 J/cm2. These data suggest that this complex and related complexes are a promising class of nonlinear optical materials.
We discuss several imaging techniques that have been studied for optical imaging through turbid media. The effectiveness of many of these techniques hinges on the nonlinear optical material used in the imaging process. We have used Rhodamine dye-doped K15 liquid crystal films in a degenerate four-wave mixing geometry in order to study the potential of this material for low-coherence imaging applications. First, we observed the dc-field-induced Freedericksz transition, which leads to a reorientational nonlinearity in our nematic liquid crystal film, and is responsible for the large optical nonlinearity that leads to phase conjugation. For our low absorbing films, this threshold voltage was on the order of 400 V/cm. Next, we show that our liquid crystal films exhibited higher phase conjugate reflectivities (0.6% maximum) for smaller beam crossing angles, which is necessary for wider field-of-views in the imaging process. Finally, we studied the time-dependent response of the phase conjugate reflectivity due to electric field assisted nonlinearities in dye-doped liquid crystal films. The motivation of these studies is to improve the imaging resolution demonstrated in our previous work.
The optical limiting performances of nine asymmetric pentaazadentate porphyrin-like metal complexes {[(R- APPC)M]Cln} have been measured at 532 nm with nanosecond pulses. In a fl38 geometry, with sample transmission of 0.51 approximately 0.80 in a 2 mm cell, the limiting thresholds for these complexes were 1.4 approximately 150.0 mJ/cm2. The throughputs of these complexes were limited to 0.31 approximately 1.42 J/cm2 for incident fluences as high as 3.5 J/cm2. The limiting throughput was strongly influenced by the nature of the ligand and metal ions. Lower bounds for the ratio of triplet excited-state to ground state absorption cross sections have been estimated at 2.3 approximately 5.7. The lower limiting thresholds, lower limiting throughputs, as well as the ease of modification of the ligands and variation of the metal ions, make these complexes promising candidates for optical power limiters.
Detailed degenerate four wave mixing (DFWM) studies of one molybdenum complex, cis-Mo(CO)4(PPh3)2 in dichloromethane (CH2Cl2) and tetrahydrofuran (THF) are reported in this paper. Upon exposure to air/oxygen, the (chi) (3) values of CH2Cl2 and THF solutions of this complex increase dramatically with time. However, when excess free ligand is added to CH2Cl2 solution of the complex, the increase in (chi) (3) value is stopped. Hence, it is possible to obtain a CH2Cl2 solution with high (chi) (3) value by first oxidizing the solution and then adding excess ligand to stabilize the solution. For THF solution, probably due to the different mechanism causing the increase of (chi) (3) values, the increase in (chi) (3) values doesn't stop even though excess free ligand is added. Further, the increase in the (chi) (3) values of both the CH2Cl2 and THF solutions parallels the increase in the linear absorption but it is unclear whether the increased linear absorption plays any role in the increase in the (chi) (3) value of the solution. This study also shows how degenerate four wave mixing can be used as a very sensitive technique to detect the chemical change in a solution when the third order optical nonlinearities of the reactant and product are very different.
We describe a coherence filtering technique in the near infrared (IR) based on degenerate four wave mixing (DFWM)
in a Barium Titanate photorefractive crystal and a dye-doped liquid crystal layer. in our experiments, we used a self modelocked
Ti:Sapphire laser and a Q-switched alexandrite laser as light sources. This technique can be used to provide
instantaneous, single-shot, two-dimensional images ofthe internal structure ofmaterials versus depth.
Nonlinear optical materials with large intensity-induced changes in refractive index and absorption, which can be
characterized by their effective third order susceptibility, are needed for numerous optical device applications. We have
reported that Mo(CO)(Ph2PX) complexes exhibit strong, non-resonantly enhanced optical nonlinearities. However, the
relationship between the structure of these complexes and their nonlinear optical properties is poorly understood. We have now
synthesized Pd(II) and Pt(II) phosphine complexes similar to the Mo(O) complexes and have studied their nonlinear optical
properties using Z-scan experiments. The Pd(II) and Pt(II) complexes have a low linear absorption at the working wavelength of
532 nm and exhibit both nonlinear optical refraction and nonlinear optical absorption effects. Our measurements indicate that the
nonlinear optical properties of these complexes depend both on the nature of the phosphine ligand and on the nature of the metal
center and its coordination geometry. However, this dependence is not as pronounced as we have previously observed in the
Mo(CO)(Ph2PX) complexes.
We describe a coherence filtering technique based on degenerate four wave mixing (DFWM) in a thin nonlinear optical material. In contrast to previous works which used ultra-short laser pulses, we performed low-coherence filtering techniques through scattering media with broad- spectrum nanosecond pulses. In our first 'proof of principle' experiments we used a 100 micrometer thick layer of dye solution as a nonlinear optical material and investigated a one dimensional case for depth-resolved measurements through a scattering media consisting of a highly scattering suspension of dielectric microspheres in water. We also describe a technique to obtain instantaneous cross-sectional images (which can be depth scanned to obtain the third dimension) performed with a low-coherence nanosecond laser source on a liquid crystal doped with an infrared dye. Experimental results were obtained with room temperature LiF:F2- and LiF:F2+ color center lasers, and a Q-switched alexandrite laser. This technique can be used to provide instantaneous, single-shot, two-dimensional images of the internal structure of materials versus depth.
We have studied the third-order nonlinearities of Ni(II) and Cu(II) metal-organic complexes in solution using wavelength tunable DFWM experiments in the 550 - 600 nm spectral region associated with d-d transitions introduced by the metal atoms. A room temperature, frequency doubled LiF:F2- color center laser was used as the tunable laser source for these experiments. Additional resonant enhancement over thermally induced nonlinearities is observed for the Cu-based metal-organic complexes in these DFWM studies. Information about the sign of the nonlinearity and relative roles of nonlinear refraction and absorption was obtained with Z-scan experiments. Energy transmission measurements indicated that nonlinear absorption occurs in all samples. Relationships between the nonlinear response and the spectral absorption features of these metal-organics are discussed.
The accurate measurement of growth parameters is essential for the development of automated, low cost silicon growth technology. The ideal growth parameter sensor for these applications is accurate, non-invasive, immune to electromagnetic interference (especially if induction heaters are used), and able to function at high temperatures. Fiber optics sensors exhibit characteristics which can meet these requirements. In this paper we report on the first use of optical low-coherence reflectometry (OLCR) for on-line, non-invasive characterization of edge-defined film-fed growth (EFG) solar silicon sheets during the actual silicon growth process. This OLCR sensor system has been used to measure vertical profiles of the thickness and flatness of one side of an EfG grown silicon octagon to an accuracy of +/- 5 micrometers . Since thickness and flatness are two important growth parameters for sheet grown silicon, the use of this non-invasive sensor for on-line silicon sheet growth monitoring may lead to improvements in solar cell manufacturing processes. In addition, this technique shows promise for providing non-invasive dimensional monitoring for a variety of other crystal types during the crystal growth process.
We have investigated nonlinear reflection and transmission processes in carbon particle suspension interfaces. Laser pulses incident on these interfaces cause plasma formation, laser induced cavitation, and the formation of a vapor layer at the dielectric interface. This vapor layer leads to optical self- switching via total internal reflection, which, in combination with other nonlinear processes such as plasma scattering, leads to optical power limiting. We will present experimental power limiting results for device prototypes based on this concept in the context of realistic optical system configurations. In addition, we have developed a theoretical model of the nonlinear reflection processes and fit this model to experimental nonlinear reflection data to determine the plasma formation threshold. The vapor interface formation time, which limits the maximum single- pulse nonlinear reflectivity, is also shown to vary as the inverse of the cube root of the carbon particle concentration. This implies that this formation time is determined primarily by the time it takes the expanding microbubbles to intersect each other and the substrate.
The macroscopic third order optical susceptibility, (chi) (3), of a series of metal free, nickel and copper containing salicyaldehyde based metal organic complexes was measured by degenerate four wave mixing at 532 nm. Insertion of the metal ion into the ligand greatly enhanced the magnitude of (gamma) , the microscopic second order molecular hyperpolarizability. Maximum (gamma) values of 2.6 X 10(superscript -29 esu were measured for the materials studied.
We report on the use of optical low coherence reflectometry for silicon characterization. The measurement system uses a low coherence light source (edge-emitting LED) in conjunction with a fiber optic Michelson interferometer. This non-contact fiber optic measurement system has been used to measure silicon thickness and flatness to an accuracy of +/- 1.5 micrometers in the laboratory.
Optical time domain reflectometry (OTDR) measurements have been performed to characterize the minimum reflection signature from PMMA plastic fiber splices. The dominant splice reflection sources due to inexact index matching and fiber core misalignment were carefully examined. A clearly detectable intrinsic OTDR reflection signature was observed with all tested fibers. The measured reflectivities varied from -54 to -27 dB. The characteristics of this signature were mapped out vs. experimental variables such as fiber surface roughness, polishing procedure, fiber-fiber alignment, and index matching characteristics.
We have investigated self-switching mechanisms in carbon microparticle suspensions. A dominant nonlinear switching mechanismin the majority ofthese samples is laserinduced cavitation which leads to total internal reflection (TIR) switching. Nonlinear reflectivities up to 90% were measured using frequency doubled, single 5ns Nd:YAG laser pulses. The fraction of energy that is not switched via 'HR undergoes additional nonlinear attenuation by nonlinear plasma scattering. We have also developed a technique for avoiding laser induced degradation of the nonlinear interface at high laser pulse energies. A simple model which may be used in the optimization of this technique is discussed.
We have investigated several nanosecond nonlinear switching mechanisms in carbon microparticle suspensions. These switching mechanisms are based on combinations of effects such as plasma scattering and cavitation-induced total internal reflection (TIR). The contributions from each of these effects is studied. The dominant nonlinear switching mechanism in the majority of these samples is laser induced cavitation which leads to TIR switching. This occurs when the incident laser energy that is absorbed by a carbon particle is sufficient to heat up and vaporize a small volume of the suspending liquid forming a microbubble. TIR switching is observed when these vapor bubbles expand to dimensions that are similar to the transverse dimensions of the incident beam and form a glass-vapor interface at the front substrate surface. Using this mechanism, nonlinear refractive index changes as large as 0.3 have been experimentally obtained on a nanosecond time scale using low power, Q-switched, frequency doubled ((lambda) equals 0.532 micrometers ), Nd:YAG laser pulses.
Optical time domain reflectometry (OTDR) measurements have been performed on polished polymethylmethacrylate (PMMA) plastic fiber splices. After the dominant splice reflection sources due to surface roughness, inexact index matching, and fiber core misalignment were eliminated, an intrinsic OTDR signature 3 - 8 dB above the Rayleigh backscatter floor remained with all tested fibers. This minimum splice reflectivity exhibits characteristics that are consistent with sub-surface polymer damage and can be used for detection of PMMA fiber splices.
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