Aligned inclusion of hemicyanine dyes into silica zeolite films for second harmonic generation

Silicalite-1 films (thickness = 400 nm) supported on both sides of glass plates (SL/G) were prepared, and hemicyanine dyes (HC-n) with different alkyl chain lengths (n, n = 3, 6, 9, 12, 15, 18, 22, and 24) were included into the silicalite-1 films by dipping SL/Gs into each methanol solution of HC-n (1 mM) for 1 d. The included numbers of HC-n per channel (N(C)) generally decreased with increasing n; that is, they were 6.4, 23.1, 15.4, 8.2, 5.7, 3.5, 0.9, and 1.2 molecules per channel, respectively. The d(33) value gradually increased with increasing n but decreased when n > 18; that is, they were 1.12, 0.50, 2.25, 3.59, 4.99, 5.30, 1.71, and 2.57 pm V(-1), respectively. However, d(33)/N(C) progressively increased with increasing n. The d(31) values were approximately 100 times smaller than the corresponding d(33) values, and the average d(33)/d(31) ratio was 109, which is higher than those of Langmuir-Blodgett (LB) films and poled polymers of nonlinear optical (NLO) dyes, by approximately 2-5 and approximately 30-50 times, respectively. The estimated average tilted angle of the dyes with respect to the channel direction was 7.7 degrees, and the calculated average order parameter was 0.97, which is approximately 480 times higher than the values observed from poled polymers. The degree of uniform alignment (DUA) generally increased with increasing n. The progressive increase of both DUA and d(33)/N(C) with n is attributed to the increase in the tendency of HC-n to enter hydrophobic silicalite-1 channels with the hydrophobic alkyl chain first. A more than 134-fold increase in DUA was observed upon increasing n from 6 to 24. The DUA of HC-24 in the silicalite-1 film reached close to 1. Although the observed d(33) values were lower than those of the LB films of NLO dyes due to very small dye densities of the silicalite films, this methodology bears a great potential to be developed into the methods for preparing practically viable NLO films.     

Sum frequency generation from Langmuir-Blodgett multilayer films on metal and dielectric substrates

Sum frequency generation (SFG) vibrational spectra of cadmium arachidate multilayer films adsorbed on a substrate with high nonresonant susceptibility, i.e., gold, and on a low nonresonant susceptibility substrate, i.e., fused quartz, have been investigated in the C-H stretching region in air. The films were formed by Langmuir-Blodgett (LB) deposition and their spectra recorded using SFG spectrometers employing both 532-nm nanosecond and 800-nm femtosecond lasers, with counter-propagating and co-propagating beam geometries, respectively. Both kinds of substrate were rendered hydrophobic by coating them with per-deuterated octadecanethiol (gold) or per-deuterated cadmium arachidate (fused quartz) monolayers. Single per-protonated arachidate layers in otherwise per-deuterated 10-layer films were used to show that the SFG resonances arise only from the topmost and lowermost layers in a LB film comprised of an even number of per-protonated layers, although the SFG spectra from the two hydrophobic substrates are different from each other. The differences in the spectra from the same ten-layer per-protonated films deposited on the two types of hydrophobic substrate have been explained in terms of a simple model that accounts for resonant and nonresonant contributions.     

Surface enhanced second harmonic generation from macrocycle, catenane, and rotaxane thin films: experiments and theory

Surface enhanced second harmonic generation (SE SHG) experiments on molecular structures, macrocycles, catenanes, and rotaxanes, deposited as monolayers and multilayers by vacuum sublimation on silver, are reported. The measurements show that the molecules form ordered thin films, where the highest degree of order is observed in the case of macrocycle monolayers and the lowest in the case of rotaxane multilayers. The second harmonic generation activity is interpreted in terms of electric field induced second harmonic (EFISH) generation where the electric field is created by the substrate silver atoms. The measured second order nonlinear optical susceptibility for a rotaxane thin film is compared with that obtained by considering only EFISH contribution to SHG intensity. The electric field on the surface of a silver layer is calculated by using the Delphi4 program for structures obtained with TINKER molecular mechanics/dynamics simulations. An excellent agreement is observed between the calculated and the measured SHG susceptibilities.     

Pure and mixed films of a nitrostilbene derivative at the air-water interface, Langmuir-Blodgett multilayer fabrication, and optical characterization

This paper reports the preparation and characterization of pure Langmuir and Langmuir-Blodgett (LB) films of a stilbene derivative containing two alkyl chains, namely 4-dioctadecylamino-4'-nitrostilbene. Mixed films incorporating docosanoic acid and the stilbene derivative are also studied. Brewster angle microscopy (BAM) analysis has revealed the existence of randomly oriented three-dimensional (3D) aggregates, spontaneously formed immediately after the spreading process of the stilbene derivative onto the water surface. These 3D aggregates coexist with a Langmuir film that shows the typical gas, liquid, and solid-like phases in the surface pressure and surface potential vs area per molecule isotherms, indicative of an average preferential orientation of the stilbene compound at the air-water interface, and a gradual molecular arrangement into a defined structure upon compression. A blue shift of 55 nm of the reflection spectrum of the Langmuir film with respect to the spectrum of a chloroform solution of the nitrostilbene indicates that two-dimensional (2D) H-aggregates are formed at the air-water interface. The monolayers are transferred undisturbed onto solid substrates with atomic force microscopy (AFM) revealing that the one layer LB films are constituted by a monolayer of the stilbene derivative together with some 3D aggregates. When the nitrostilbene compound is blended with docosanoic acid, the 3D aggregation is avoided in the Langmuir and Langmuir-Blodgett films, but does not limit the formation of 2D H-aggregates, desirable for second-order nonlinear optical response in the blue domain. The AFM images of the mixed LB films show that they are formed by a docosanoic acid monolayer and, on the top of it, a bilayer of the stilbene derivative.     

Origin of the photoinduced optical second harmonic generation arising in N-phenyl microcrystalline films

Photoinduced second-order nonlinear optical effects, particularly optical second harmonic generation (SHG) of N-phenyls with different numbers of aromatic rings deposited on glass substrates were studied. As a fundamental beam, a 5-ps pulsed Nd:YAG laser was used. Quantum chemical time-dependent density functional theory (TDDFT) simulations of the nonlinear optical properties were performed. The first-order hyperpolarizabilities of isolated molecules were calculated, under the influence of a polarized pumping beam, to evaluate the role played by the nanointerfaces separating the microcrystallites and the amorphous environment. Consideration was performed within a framework of steady-state Langevin order parameters for amorphous-like films. A strong dependence of the photoinduced SHG versus the number of aromatic rings determining the degree of film crystallinity was shown. A comparison of experimental data and theoretically evaluated results shows that for the photoinduced first-order nonlinear optical effect the dominant contribution is an amorphous-like structural component, unlike the transport properties, where the crucial role is played by the nanointerface region. This may reflect a specific feature of the multiphoton processes in such types of nanointerfaces because of nanoconfined effects.     

Surface studies of polyimide thin films via surface-enhanced Raman scattering and second harmonic generation

Two polyimides having the same backbone chemical structure and different pendant side groups at the 2- and 2′-positions of the diamine, the six methylene units capped with 4-cyanobiphenyl end groups and trifluoromethyl, were synthesized (6FDA-6CBO and 6FDA-PFMB). Surface-enhanced Raman scattering and surface optical second harmonic generation measurements show that after rubbing the major change in 6FDA-PFMB surface appears in the orientation of the dianhydride, which was originally planar, but becomes tilted with respect to the surface plane. In the case of 6FDA-6CBO, rubbing also causes the originally planar 4-cyanobiphenyls to tilt away from the surface and assume an azimuthally anisotropic distribution.     

Organization and orientation of amphiphilic push-pull chromophores deposited in Langmuir-Blodgett monolayers studied by second harmonic generation and atomic force microscopy

Orientation and organization of two amphiphilic push-pull chromophores mixed with two phospholipids (dipalmitoylphosphatidylcholine and dioleoylphosphatidylcholine) in Langmuir-Blodgett (LB) monolayers are investigated by second harmonic generation. The LB monolayers have also been characterized by atomic force microscopy and UV-vis spectroscopy. The effective molecular orientations and hyperpolarizabilities of the chromophores are studied as a function of the phospholipid concentrations. The experimental results are discussed within the frame of a model of orientational distribution of the chromophores which gives the orientational mean angle and bounds on the orientational disorder. The mean orientation of the chromophores is found to be within 45-55 degrees whereas their hyperpolarizability coefficients, measured with respect to quartz, are estimated to be in the range (0.3-0.7) x 10(-27) esu taking account of the maximal orientational disorder.     

Surface enhanced fluorescence and Raman imaging of Langmuir-Blodgett azopolymer films

The spectroscopic properties and surface-enhanced spectra of Langmuir-Blodgett (LB) films of methacrylic homopolymer (HPDR13) are presented. It is shown that LB film displays strong fluorescence attributed to the spatial restrictions imposed by its structure. The emission is observed in conjunction with photoisomerization, a process clearly demonstrated by the formation of surface-relief gratings in the LB film [C.R. Mendon?a et al., Macromolecules 32 (1999) 1493]. Surface-enhanced Raman scattering (SERS), Surface-enhanced resonance Raman scattering (SERRS) and surface-enhanced fluorescence (SEF) were observed for LB films of HPDR13 deposited onto silver island films. SERS measurements were also carried out on a sample fabricated with one monolayer LB film deposited onto silver islands followed by one overlayer of silver (LB sandwiched between two layers of silver islands). The polymer interacts very weakly with the metal surface (physisorption), and the enhancement effect is determined by the local electric field enhancement. The strong SERS and SERRS signals were suitable for micro-Raman imaging. Line, area mapping and global images of the LB monolayer on silver island are reported. The transfer ratio in the fabrication of the LB suggests a homogeneous coating of the silver islands, thereby the chemical images show the variation of the SERS intensity due to surface enhancement.     

Invited Lecture. Studies of liquid crystal monolayers and films by optical second harmonic generation

It is shown that optical second harmonic generation can be used to probe a number of important properties of liquid crystals: second order non-linearity of liquid crystal molecules, polar ordering and orientation of liquid crystal monolayers at various interfaces, and bulk alignment of molecules in supported and freely suspended films. Surface effects on bulk alignment can also be investigated.     

Synthesis and second harmonic generation studies of nlo-functionalized polyimides

Several NLO-functionalized polyimides were synthesized through novel synthetic pathways and their NLO properties were characterized. For preventing the disadvantage in poly(amic acid) precursor route, the Mitsunobu reaction and alternative synthetic route for NLO polyimides were chosen. The second-order NLO coefficients (χ⁽²⁾) of the synthesized polyimides were between 48pm/V and 122pm/V. The thermal stability of nonlinearity characterized showed that all polyimide films retain their NLO activities at temperatures below 100°C.     

Hydrogen-bonding contributions to the lattice energy of salts for second harmonic generation

The lattice energies of a series of organic dihydrogenphosphate salts capable of second harmonic generation (SHG) have been calculated. These calculations, coupled with empirical data, indicate that a minimum of 20–25% of the lattice energy arises from hydrogen-bond interactions. Hydrogen bonding is shown to be a strong enough force to have a profound effect on the overall packing and crystal geometry of such ionic materials, and is thus an important factor to consider for crystal engineering.     

Preparation and characterization of mono- and multilayer films of polymerizable 1,2-polybutadiene using the Langmuir-Blodgett technique

The essence of this study is to apply the Langmuir-Blodgett (LB) technique for assembling asymmetric membranes. Accordingly, Langmuir films of a (further) polymerizable polymer, 1,2-polybutadiene (1,2-pbd), were studied and transferred onto different solid supports, such as gold, indium tin oxide (ITO), and silicon. The layers were characterized both at the air/water interface as well as on different substrates using numerous methods including cyclic voltammetry, impedance spectroscopy, spectroscopic ellipsometry, atomic force microscopy, X-ray photoelectron spectroscopy, and reflection-absorption Fourier transform infrared spectroscopy. The Langmuir films were stable at the air-water interface as long as they were not exposed to UV irradiation. The LB films formed disorganized layers, which gradually blocked the permeation of different species with increasing the number of deposited layers. The thickness was ca. 4-7 ? per layer. Irradiating the Langmuir films caused their cross-linking at the air-water interface. Furthermore, we took advantage of the reactivity of the double bond of the LB films on the solid supports and graft polymerized acrylic acid on top of the 1,2-pbd layers. This approach is the basis of the formation of an asymmetric membrane that requires different porosity on both of its sides.     

Preparation and nonlinear optical properties of novel Y-type polyesters with highly enhanced thermal stability of second harmonic generation

3,4-Di-(2′-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and condensed with terephthaloyl chloride and adipoyl chloride to yield novel Y-type polyesters (4-5) containing 3,4-dioxybenzylidenemalononitrile groups as NLO-chromophores, which constituted parts of the polymer main-chains. The resulting polymers 4-5 are soluble in common organic solvents such as acetone and N,N-dimethylformamide. They showed thermal stability up to 300 °C in thermogravimetric analysis with glass-transition temperatures obtained from differential scanning calorimetry in the range 89-91 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at the 1064 nm fundamental wavelength were around 2.47 pm/V. The dipole alignment exhibited high thermal stability even at 10 °C higher than T_g, and there is no SHG decay below 100 °C due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.     

In-situ poling and synthesis of NLO chromophore-bearing polyurethanes for second harmonic generation

The preparation of six diol and one triol monomers bearing donor–acceptor chromophores is described. The monomers contain the N,N′-bis(2-hydroxyethyl)aniline unit with various acceptor groups attached in some cases via azo or olefin linkages, at the para position. Acceptors studied include nitro, tricyanovinyl, cyclobutene-1,2-dione, and imidazolidine-2,4-dione. Poled polymer films were prepared by thermal polymerization of these with 2,4-toluenediisocyanate (TDI) in the presence of an electric field generated by a corona tip. The resulting thin (ca. 1 μm), glassy polymer films were shown to exhibit reasonably good second harmonic generation efficiencies. Preliminary results show that the polymers with higher T_g's have the best temporal stability. The polymer derived from the diol bearing an imidazolidine-2,4-dione acceptor shows only a ca. 30% decrease in its second harmonic generation (SHG) signal over 200 days at room temperature, even though it is not crosslinked. We attribute this to hydrogen bonding interactions from the urethane and imidazolidine-2,4-dione groups. A crosslinked film derived from the triol and TDI has an exceedingly stable SHG response at room temperature, and no decrease in the SHG response is observed at 100°C for a few hours. © 1993 John Wiley & Sons, Inc.     

Second harmonic generation at the interface of copper tetra-tert-butyl phthalocyanine Langmuir-Blodgett film/metal

As one of the most primitive nonlinear optical phenomena, optical second harmonic genera-tion (SHG) has been investigated for half a century and it has become a very useful spectroscopic tool in the study of surface and interface[1—3]. It was theoretically shown that the SH signal cannot be generated in a centrosymmetric system. However, the generation of SH signal from the centro-symmetric molecules such as fullerene (C60) and CuPc has been detected[4—7]. In our recent ex-periments, an …     

A second harmonic generation study of the oxidation of copper electrodes

The oxidation of copper in basic media has been studied by in situ second harmonic generation (SHG), where the SHG signal was recorded alongside the cyclic voltammogram. The SHG signal changes markedly as the copper surface is oxidised to first Cu₂O and then CuO in a duplex structure. The development of Cu₂O gives rise to a resonant SHG signal because of the band-gap of the material then the upper CuO layer produces an electric-field induced second harmonic (EFISH) response. A correlation of charge with the SHG signal is informative with regard to the mechanism of reduction of CuO and SHG is shown to be a useful method for the examination of oxidation of electrode surfaces.     

Second-order nonlinear optical properties of side-chain liquid crystalline polymers studied by second harmonic generation from thin films

The two independent elements of the second-order nonlinear optical susceptibility tensor of a range of contact poled, donor–acceptor substitued side-chain polymers are reported. The susceptibilities were measured by second harmonic generation from thin films, typically less than 0.5 μm thick, at a fundamental wavelength of 1064 nm. The largest value was χ = 2.64 pm/V which is three times greater than the χ value of KDP and was measured in a nitrobenzylidene side chain, polyhydroxystyrene polymer with an eleven unit alkyl chain spacer attaching the side group to the backbone. Typical susceptibility values obtained were χ～0.3 pm/V and X⁽²⁾₃₃～1 pm/V. The coherence lengths of the materials, which lay in the range 4–12 μm, were measured at 1064 nm by the maker fringe technique using thick, wedge-shaped samples.     

Infrared spectroscopy analysis of the structure of multilayer Langmuir-Blodgett films: effect of deposition velocity and pH

Multiple Langmuir-Blodgett (LB) films of arachidic acid were deposited on germanium (Ge) substrates from subphase solutions of 10(-4) M CdCl2 at different pH values and at different deposition speeds. Attenuated total reflectance infrared (ATR-IR) spectroscopy was used to obtain information on the molecular order and structure of these multilayer LB films. At pHs higher than the pKa of the fatty acid/cation system, transfers took place only during the downstroke, indicating X-type deposition. At pH = pKa and large deposition speeds, deposition partially failed during the downstroke, resulting in Z-type depositions. Analysis of the infrared spectra indicates that multiple LB films deposited only during the upstroke (Z-type) or during downstrokes (X-type) have a centrosymmetric structure typical of films deposited during the upstroke and downstroke, except for a slight decrease in molecular order and tilt angle as the pH increases (X-type). The centrosymmetric structure indicates that rearrangement of layers takes place between cycles. Experimental evidence of such rearrangement occurring in a fatty acid/divalent cation salt subphase is shown here, and rearrangement alternatives are discussed.     

Polyelectrolyte layer-by-layer self-assembly enhanced by electric field and their multilayer membranes for separating isopropanol–water mixtures

An electric field enhanced method is developed for fabricating layer-by-layer (LbL) self-assembly polyelectrolyte multilayer membranes. Three kinds of electric field enhanced polyelectrolyte multilayer membranes (EPEMs), poly(diallyl dimethylammonium chloride)/poly(styrenesulfonate sodium salt) (PDDA/PSS), poly(diallyldimethylammonium chloride)/poly(acrylic acid sodium salt) (PDDA/PAA) and polyethylenimine/poly(acrylic acid sodium salt) (PEI/PAA), were self-assembled on a reverse osmosis membrane (ROM). The pervaporation performances of EPEMs for separating isopropanol–water mixtures (90/10, w/w) are all superior to those of corresponding normal self-assembled polyelectrolytes membranes (PEMs), and the selectivity increases with PDDA/PSS, PDDA/PAA and PEI/PAA in order. For (PEI/PAA)₄PEI EPEM, the separation factor is 1075 and permeation flux is 4.05 kg m⁻² h⁻¹ at 70 °C. This novel method speeds up the LbL process, which makes it promising for the practical application of the LbL multilayer membrane.     

Ellipsometric approach for the real-time detection of label-free protein adsorption by second harmonic generation

Second harmonic generation (SHG) was performed using a novel ellipsometric detection approach to selectively probe the real-time surface binding kinetics of an unlabeled protein. The coherence of nonlinear optical processes introduces new possibilities for exploiting polarization that are unavailable with incoherent methods, such as absorbance and fluorescence. Adsorption of bovine serum albumin (BSA) at silica/aqueous solution interfaces resulted in changes in the polarization state of the frequency-doubled light through weak, dynamic interactions with a coadsorbed nonlinear optical probe molecule (rhodamine 6G). Using a remarkably simple instrumental approach, signals arising exclusively from surface interactions with BSA were spatially isolated and selectively detected with high signal-to-noise. The relative intensities acquired during the kinetics experiments using both circularly and linearly polarized incident beams were in excellent agreement with the responses predicted from SHG ellipsometry polarization measurements. Analysis of the polarization-dependent SHG generated during BSA adsorption at glass/aqueous solution interfaces provided direct evidence for slow conformational changes within the protein layer after adsorption, consistent with protein denaturation. This polarization selection approach is sufficiently general to be easily extended to virtually all coherent nonlinear optical processes and a variety of different surface interactions and architectures.