As an amorphous material with full inversion symmetry, silica-based microstructures cannot possess significant secondorder nonlinearity. We recently developed a method that can potentially overcome this deficiency by coating a silica fiber taper with layers of radially aligned nonlinear molecules. The coating process can be accomplished through layerby- layer self-assembly, where the alignment of the nonlinear molecules is maintained through electrostatic interaction. As a result, the nonlinear fiber structures are thermodynamically stable and can generate significant second-order nonlinear responses despite their full rotational symmetry. This prediction has been experimentally confirmed through SHG measurements. To further enhance the overall second-order nonlinearity, we have developed an UV-ablation-based approach that can generate second-order nonlinearity that is spatially periodic along the fiber taper. Our preliminary experiments suggest that SHG intensity can be enhanced by such quasi-phase-matching configurations.
We can also use the self-assembly approach to construct tunable plasmonic systems. As a proof-of-concept study, we assembled swellable polymer films over a planar Au substrate through layer-by-layer assembly and covered the swellable polymer with a monolayer of quantum dots. After immersing the swellable plasmonic structure in solution and adjusting its pH value, we used a fluorescence lifetime based approach to demonstrate that the thickness of the swellable polymers can be modified by almost 400%. The fluorescence lifetime measurements also confirmed that the plasmonic resonance can be significantly modified by the swellable polymers.
We investigate the influence of ionic liquids on the electromechanical performance of Ionic Polymer Conductor Network
Composite (IPCNC) bending actuators. Two imidazolium ionic liquids (ILs) with one cation, which is 1-ethyl-3-
methylimidazolium ([EMI+]), and two different anions, which are tetrafluoroborate ([BF4-]) and
trifluoromethanesulfonate ([Tf-]), are chosen for the study. By combining the time domain electric and
electromechanical responses, we developed a new model that describes the ion transports in IPCNC actuators. The time
constant of excess cation and anion migration in various composite electrodes are deduced: 6s and 25s in RuO2/Nafion;
7.9s and 36.3s in RuO2/Aquivion; 4.8s and 53s in Au/PAH, respectively. NMR is also applied to provide quantitative
measures of self-diffusion coefficients independently for IL anions and cations both in pure ILs and in ILs absorved into
ionomers. All the results indicate that the motion of cation, in the studied pure ionic liquids, polymer matrix and
conductor network composites, is faster than that of anion. Moreover, the CNC morphology is playing a crucial role in
determining the ion transport in the porous electrodes.
Traditional ionic polymer/conductor network composite (IPCNC) electromechanical actuators exhibit low actuation
speed and efficiency. In order to improve these parameters while still maintaining low voltage operation, we investigated
IPCNC with a range of composite layer (active layer) and middle ionomer layer (passive layer) thicknesses. We show
that it is the slow ion transport in the porous composite electrode layer that limits the actuation speed of IPCNCs. By
reducing the thickness of the composite electrode layers, both the actuation speed and efficiency can be improved.
Moreover, we show that the IPCNC actuator speed and efficiency are intimately related to the morphology of the
composite electrode layer and the conductor network composites fabricated by ionic self-assembled layer-by-layer
(LBL) exhibit higher strain response compared with that from the traditional IPCNC. For example, LBL composites
show very high intrinsic strain of about 7%. Detailed device analysis points out directions of further improvement of
these actuators.
The development of both “soft” and “hard” fabrication techniques for the patterning of nonlinear photonic devices in ionically self-assembled monolayer (ISAM) films is reported. A combination of electron beam lithography and reactive ion etching was used to pattern two-dimensional holes with a lattice of 710 nm and diameters ranging from 550 to 650 nm. A soft alternative to this fabrication was also demonstrated. Nanoimprint lithography was successfully employed to pattern similar photonic structures with average hole diameters of 490 nm and a lattice spacing of 750 nm, as well as Bragg gratings with a period of 620 nm. Potential impact of this fabrication process on the chemical composition and nonlinear properties of the ISAM films was assessed using Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy, and second harmonic generation. The spectroscopy techniques confirmed that the chemical composition and bonding of the ISAM films was not adversely affected by the thermal cycles required for nanoimprinting. Second harmonic generation analysis also confirmed that the nanoimprinting process did not affect the nonlinear properties of the material, PCBS/PAH ISAM films, further indicating the suitability of such materials for the nanoimprinting of nonlinear optical photonic structures.
Antireflection coatings have been fabricated by self-assembly using silica nanoparticles. The ionic self-assembled
multilayer (ISAM) films are tightly packed and homogeneous. While the geometric properties of a
matrix of spherical particles with corresponding void interstices are highly suitable to meet the conditions for
minimal reflectivity, it is also a cause for the lack of cohesion within the constituent body, as well as to the
substrate surface. This study investigates methods for improving the interconnectivity of the nanoparticle
structure. One such method involves UV curing of diazo-resin (DAR)/silica nanoparticle films, thereby
converting the ionic interaction into a stronger covalent bond. Factorial analysis and response surface
methods are incorporated to determine factors that affect film properties, and to optimize their optical and
adhesive capabilities. The second study looks at the adhesive strength of composite multilayer films. Films
are fabricated with silica nanoparticles and poly(allylamine hydrochloride) (PAH), and dipped into aqueous
solutions of PAH and poly(methacrylic acid, sodium salt) (PMA) to improve cohesion of silica nanoparticles
in the matrix, as well as binding strength to the substrate surface. The results of the two studies are discussed.
Ionic self-assembled multilayers (ISAMs) adsorbed on long period fiber gratings (LPGs) can serve as an inexpensive,
robust, portable, biosensor platform. The ISAM technique is a layer-by-layer deposition technique that creates thin films
on the nanoscale level. The combination of ISAMs with LPGs yields exceptional sensitivity of the optical fiber
transmission spectrum. We have shown theoretically that the resonant wavelength shift for a thin-film coated LPG can
be caused by the variation of the film's refractive index and/or the variation of the thickness of the film. We have
experimentally demonstrated that the deposition of nm-thick ISAM films on LPGs induces shifts in the resonant
wavelength of > 1.6 nm per nm of thin film. It has also been shown that the sensitivity of the LPG to the thickness of the
ISAM film increases with increased film thickness. We have further demonstrated that ISAM-coated LPGs can function
effectively as biosensors by using the biotin-streptavidin system and by using the Bacillus anthracis (Anthrax) antibody-
PA (Protective Antigen) system. Experiments have been successfully performed in both air and solution, which
illustrates the versatility of the biosensor. The results confirm that ISAM-LPGs yield a reusable, thermally-stable, and
robust platform for designing and building efficient optical biosensors.
In this paper we present a study of thermally interdiffused poly (3-octylthiophene) (P3OT) - C60 photovoltaic devices of varying polymer and fullerene layer thicknesses. It is found that overall device performance and external quantum efficiencies (EQEs) in the wavelength region of peak absorption are enhanced for thinner polymer as well as thinner fullerene layers. We present a simple, first level model for EQE curves that accounts for the effects of absorption throughout the film. The model considers 3 distinct regions; pure donor, interdiffused donor and acceptor, and pure acceptor. It is found that this model reproduces quite effectively the experimentally observed shapes and relative magnitudes for varying donor thickness when compared with a similar experimental study. It also reproduces the shapes of the EQE curves but is not as effective in reproducing the relative magnitudes for varying fullerene thickness devices.
We have shown that ionic self-assembled multilayers (ISAMs) deposited on optical fiber long period gratings (LPGs) yield dramatic resonant-wavelength shifts, even with nanometer-thick films. Precise control of the refractive index and the thickness of these films was achieved by altering the relative fraction of the anionic and cationic materials combined with layer-by-layer deposition. We demonstrate the feasibility of this highly controllable deposition-technique for fine-tuning grating properties for grating applications. In addition, we confirm theoretically that the resonant wavelength shift can result from either the variation of the thickness of the film and/or the variation of its refractive index. Finally, we demonstrate that ISAMs adsorbed on LPGs function effectively as biosensors. These simulations and experimental results confirm that ISAM-coated-LPGs provide a thermally-stable, reusable, robust, and attractive platform for building efficient fiber optic sensors and devices.
The interface between polymer and fullerene in organic photovoltaic devices is improved by thermally induced interdiffusion. Starting from a bilayer of 2-methoxy-5-(2’-ethylhexyloxy)-1,4-phenylenevinylene copolymer (MEH-PPV) and the Buckminsterfullerene (C60) devices are heated in the vicinity of the glass transition temperature creating a gradient bulk-heterojunction. Interdiffused devices show photoluminescence quenching with concomitant improvements in photocurrents. Variation of the polymer layer thickness shows an increase in photocurrents with decreasing layer thickness within the examined thickness regime as transport of the separated charges out of the device is improved. The interdiffusion was observed in situ by monitoring the photocurrents during the heating step. Cross-sectional transmission electron microscopy reveals C60 clusters of up to 30 nm in diameter in the interdiffused devices. The clustering of the fullerene molecules puts a significant constraint on the interdiffusion process.
Recently, ionically self-assembled monolayers (ISAMs) of polymers with nonlinear optical chromophores have been shown to spontaneously exhibit a preferential ordering during the deposition process. This gives rise to a substantial second order nonlinear optical (NLO) response. Here, we use this second harmonic generation (SHG) to our advantage in the in situ study of the deposition of ISAMs. Upon immersion in the NLO-active polyelectrolyte solution, the SHG rises sharply over the first minute, demonstrating a rapid adsorption process. Immersion in the NLO-inactive partner polyelectrolyte leads to an instantaneous reduction in the SHG signal. We also show that the adsorption and ordering of a noncentrosymmetric nonlinear optical polymer increases with increasing PCBS concentration. These studies provide deeper understanding of the processes by which noncentrosymmetric order is formed in ISAM films and allows design of improved self-assembled nonlinear optical materials.
Ionically self-assembled monolayer (ISAM) films have been shown to spontaneously produce noncentrosymmetric ordering that gives rise to a substantial second order nonlinear optical (NLO) response. Typically, the ISAM films for NLO response are an assemblage of bilayers of oppositely charged polymers whose thickness can be controlled through variation of pH and ionic strength of the immersion solutions. Ordinarily, the NLO-inactive polycation solution parameters are chosen the same as for the NLO-active polyanion solution. Here, we study the effects of varying the polycation solution parameters separately from the polyanion solution. We also investigate the effects of replacing the NLO-active polymer layers with layers of dianionic molecules. Films fabricated exclusively using polyelectrolytes contain some fraction of both randomly oriented and anti-parallel oriented chromophores. We have examined the incorporation of dianionic chromophores into ISAM films in order to increase the net polar orientation of the chromophores and reduce bilayer thickness.
Ionically self-assembled monolayers (ISAMs), fabricated by alternate adsorption of cationic and anionic components, yield exceptionally homogeneous thin films with sub- nanometer control of the thickness and relative special location of the component materials. Using organic electrochromic materials such as polyaniline, we report studies of electrochromic responses in ISAM films. Reversible changes in the absorption spectrum are observed with the application of voltages on the order of 1.0 V. Measurements are made using both liquid electrolytes and in all-solid state devices incorporating solid polyelectrolytes such as poly(2-acylamido 2-methyl propane sulfonic acid) (PAMPS). Due to the precise nanometer scale control of thickness and composition of the electrochromic composite system, switching times faster than 50 ms have been demonstrated.
We report the fabrication of thin organic layers and photovoltaic devices made from them. Building thin layers of organic materials via the method of ionically self-assembled monolayers provides control over the layer thickness and composition of multilayer structures on a nanometer scale. This allows to accurately dope a photoluminescent host material with energy or charge accepting guests, changing the emissive character of the pure photoluminescent host film to a predominantly non-emissive, charge generating structure. We show that by varying the concentration of the guest Copper phthalocyanine and C60(OH)2 in poly- (para-phenylene-vinylene) we can measure the energy migration as well as dissociation of the exciton and can determine the lifetime and the diffusion radius of the exciton. Increasing the number of dopands in the host material, the photoluminescence emission spectra shift and decrease in intensity reflecting a decrease in the number of excitons transferring to neighboring chains or conjugation segments. For high dopand concentrations the recombination of excitons only happens on the same chain as the generation. Building a device to achieve the optimal guest/host ratio for optimal exciton dissociation is one important step in the design of high efficiency photovoltaic devices.
Polymeric films fabricated from ionically self-assembled monolayers (ISAMs) spontaneously from in a noncentrosymmetric structure requisite for a nonzero second order nonlinear optical (NLO) susceptibility, (chi) (2), without the need for electric field poling. ISAM NLO films exhibit excellent long-term temporal stability of (chi) (2), having shown no decay over a period of nearly three years. They are also remarkably stable at elevated temperatures. While (chi) (2) decreases by 20 percent as the temperature is raised to 150 degrees C, total recovery of the susceptibility is observed upon cooling, demonstrating that the decrease is not due to an irreversible randomization of the chromophore alignment. The thickness, orientational order, and NLO response are found to be strongly dependent on the pH and ionic strength of the solutions form which the films are deposited. The largest (chi) (2) values are observed in films with the smallest bilayer thickness. This suggests that polar orientation is obtained primarily at the interfaces between adjacent layers rather than throughout a full monolayer.
We present detailed studies of polymer light emitting diodes fabricated from ionically self-assembled monolayer thin films. The ionically self-assembled monolayer (ISAM) films are created with a new thin film fabrication technique that allows detailed structural and thickness control at the molecular level. The ISAM fabrication method simply involves the dipping of a charged substrate alternately into polycationic and polyanionic aqueous solutions at room temperature. Importantly, the ISAM technique yields exceptionally homogeneous, large area films with excellent control of total film thickness. Our studies concentrate on improving the performance of ISAM light emitting diodes that include poly(para-phenylene vinylene) (PPV). The individual thickness of each monolayer and the interpenetration of adjacent layers can be precisely manipulated through the parameters of the electrolyte solutions. The effects of the pH and ionic strength of the immersion solutions, the total film thickness, and the PPV thermal conversion parameters on the photoluminescence and electroluminescence yields have been systematically studied. Through the ISAM process we can also deposit well-defined thicknesses of different polymers at the indium tin oxide and aluminum electrode interfaces. The interface layers are found to affect the electroluminescence efficiency.
Charles Brands, T. Piok, Patrick Neyman, A. Erlacher, C. Soman, M. Murray, Raoul Schroeder, James Heflin, Wilhelm Graupner, Daniela Marciu, Adam Drake, Michael Miller, Hong Wang, Harry Gibson, Harry Dorn, Guenther Leising, M. Guzy, Rick Davis
We use the technique of ironically self-assembled monolayers (ISAMs) to produce photovoltaic devices of well-controlled thickness and composition. The ISAM nanostructure fabrication method simply involves the alternate dipping of a charged substrate into aqueous cationic and anionic solutions at room temperature. We have employed several approaches to combine the tetrahydrothiophenium precursor of PPV with fullerenes and other organic materials .We apply modulation spectroscopy for the electro-optical characterization of the ISAM-devices. Analyzing the thickness dependence of the recorded photocurrent action spectra allows us to identify the photoactive region within the devices. The modulation frequency dependence of the photocurrent can be assigned to the influence of trapped charges taking part in the photovoltaic process. By utilizing the ability to control both thickness and composition of the organic layer at a nanometer level of precision, the composition and concentration of these defects has ben systematically varied.
We report that anew ionically self-assembled monolayer (ISAM) method for thin-film deposition can be employed to fabricate materials possessing the noncentrosymmetry that is required for a second order, (Chi) (2), nonlinear optical response. Using several different commercially- available polyelectrolytes and additional precursors designed and fabricated in our laboratories, we have produced ISAM nonlinear optical thin films with (Chi) (2) films self-assemble into a noncentrosymmetric structure that has exhibited no measurable decay of (Chi) (2) at room temperature over a period of more than four months. The (Chi) (2) of ISAM thin-films has been examined by second harmonic generation using a fundamental wavelength of 1200 nm. The second harmonic intensity of the films exhibits the expected quadratic consistent with orientation of the chromophobe dipole moment perpendicular to the substrate. We describe the potential application of such NLO thin-film materials in field sensing elements and support instrumentation systems.
We demonstrate, for the first time, that a new ionically self-assembled monolayer (ISAM) technique for thin film deposition can be employed to fabricate materials possessing the noncentrosymmetry that is requisite for a second order, nonlinear optical response. Using two different commercially-available polyelectrolytes, we have
produced ISAM nonlinear optical thin films with values comparable to that of quartz. As a result of the ionic attraction between successive layers, the ISAM films self-assemble into a noncentrosymmetric structure that has exhibited no measureable decay of at room temperature over a period of more than four months. The x2 of ISAM films has been examined by second harmonic generation using a fundamental wavelength of 1200 nm. The second harmonic intensity of the films exhibits the expected quadratic dependences on fundamental intensity and film thickness while the polarization dependence is consistent with orientation of the chromophore dipole moment perpendicular to the substrate.
The optical limiting performance of C60 is shown to be extended to longer wavelengths by derivatization of
the fullerene. While the reverse saturable absorption behavior of C60 generally improves at wavelengths longer than
532 nm due to decreased ground state absorption and increased excited state absorption, the peak of the triplet-triplet
excited state absorption at 750 nm is inaccessible as a result of the near complete transparency of C60 beyond 650
nm. Partial breaking of the spherical it-conjugation by attached substituents leads to increased ground state
absorption cross-sections in the appropriate wavelength range. The peak of the triplet-triplet absorption is shifted to
700 nm in the C60 derivatives, resulting in exceptionally strong optical limiting in this spectral region.
We report two separate studies of the nonlinear optical properties of unique fullerene materials. Degenerate four- wave mixing measurements of the endohedral metallofullerene Er2 at C82 at 1064 nm show that the third order susceptibility is increased by more than two orders of magnitude relative to the empty cage fullerenes as a result of the metal-to-cage charge transfer. Optical limiting studies of C60 derivatives and higher fullerenes in the 680 to 880 nm spectral region demonstrate that these materials are strong reverse saturable absorbers at wavelengths where C60 itself is transparent. The tremendous variety of available fullerene-derived structures provides important opportunities for optimization of nonlinear optical responses.
The wavelength-dependence of optical limiting in the reverse saturable absorber C60 has been studied in detail over a large spectral range and compared to that of two phthalocyanines. The reverse saturable absorption of C60 is found to increase at wavelengths longer than the standardly measured 532 nm. The optical limiting data have been analyzed in terms of the dynamical population rate equations to obtain the excited state absorption cross-sections. The computational effort of the analysis is greatly reduced by a semi-analytic solution to the rate equations that we have developed. We have also demonstrated that the spectral window for optical limiting of fullerenes can be increased to include longer wavelengths at which C60 is transparent. Both a C60 charge-transfer complex and C76 have been shown to exhibit strong reverse saturable absorption at long wavelengths.
Earlier, we had shown how electron correlation effects in ?-electron virtual
excitation processes determine the large, ultrafast nonresonant nonlinear optical
responses of conjugated organic and polymeric materials1-3.
In this paper, we summarize detailed measurements of the frequency dependence of (gamma) ijkl(-(omega) 4;(omega) 1,(omega) 2,(omega) 3) for the third-order nonlinear optical processes dc-induced second harmonic generation (DCSHG) and third harmonic generation (THG) by wedge Maker fringe techniques recently completed for several important linear polyene structures.
In atoms and molecules, nonresonant second-order and third-order optical processes mediated by virtual electronic excitations are described by their second-order (beta) ijk(-(omega) 3;(omega) 1,(omega) 2) and third-order (gamma) ijkl(-(omega) 4;(omega) 1,(omega) 2,(omega) 3) optical susceptibilities, respectively. In general, the real population of the initial state for the virtual electronic excitations can be either the usual singlet ground state S0 or an optically pumped excited state Sn. The authors have found for quasi-one (1-D) and quasi-two (2-D) dimensional chain-like and disc-like structures, compared to the ground state, the nonresonant excited state (beta) ijkSn(-(omega) 3;(omega) 1,(omega) 2) or (gamma) ijklSn(-(omega) 4;(omega) 1,(omega) 2,(omega) 3) can markedly increase, and even change sign, when the first (S1) or second (S2) (pi) -electron excited state is optically pumped and populated for timescales sufficiently long to allow nonresonant measurements of (beta) ijkSn(-(omega) 3;(omega) 1,(omega) 2) or (gamma) ijklSn(-(omega) 4;(omega) 1,(omega) 2,(omega) 3).
A general enhancement mechanism is reviewed for nonlinear optical processes originating from
real population of electronic excited states. The nonresonant third order optical susceptibility
y1(-w4;wi,w2,w3) of quasi-one dimensional conjugated linear chains can be enhanced by orders
of magnitude, or even change sign, when the first (S1), or second (52), electronic excited state is
optically pumped and then populated for times suitably long to perform nonresonant measurements
of y1(-w4; w1 , w2,w3) at frequencies different from the resonant pump frequency.
Since the basic phthalocyanine structure intrinsically possesses high thermal and
oxidative stabilities, phthalocyanines incorporated into sol-gel glasses provide an attractive
approach for realizing highly stable nonlinear optical media. Experimental results recently
obtained for the nonresonant and resonant third order optical properties of
metallophthalocyanines are reviewed in this paper.
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