Light induced refractive index changes in PMMA films doped with styrene

Solutions of poly(methyl methacrylate) in styrene are used to produce thin polymer films (1m–20m) saturated with styrene monomer. In the illuminated areas refractive index changes up to 10^–2 are achieved by photoinduced polymerisation. The index patterns may be fixed by annealing treatments removing the residual monomer.We thank P. Hertel, M. Kopietz, M. D. Lechner and D. Steinmeier for valuable discussions. Financial support of the Stiftung Volkswagenwerk is gratefully acknowledged.     

Reactivity of methemoglobin immobilized on TiO2 nanoparticle films

Facile demetallation occurs upon contact of the methemoglobin with a mesoporous TiO2 host in phosphate buffer media at pH 5.5 but not in acetate buffer media. As a result, voltammetric signals previously attributed to hemoglobin-based redox processes have to be re-interpreted.     

Redox-active ionic-liquid-assisted one-step general method for preparing gold nanoparticle thin films: applications in refractive index sensing and catalysis

We describe a general one-step facile method for depositing gold nanoparticle (GNP) thin films onto any type of substrates by the in situ reduction of AuCl(3) using a newly designed redox-active ionic liquid (IL), tetrabutylphosphonium citrate ([TBP][Ci]). Various substrates such as positively charged glass, negatively charged glass/quartz, neutral hydrophobic glass, polypropylene, polystyrene, plain paper, and cellophane paper are successfully coated with a thin film of GNPs. This IL ([TBP][Ci]) is prepared by the simple neutralization of tetrabutylphosphonium hydroxide with citric acid. We also demonstrate that the [TBP][Ci] ionic liquid can be successfully used to generate GNPs in an aqueous colloidal suspension in situ. The deposited GNP thin films on various surfaces are made up of mostly discrete spherical GNPs that are well distributed throughout the film, as confirmed by field-emission scanning electron microscopy. However, it seems that some GNPs are arranged to form arrays depending on the nature of surface. We also characterize these GNP thin films via UV-vis spectroscopy and X-ray diffractometry. The as-formed GNP thin films show excellent stability toward solvent washing. We demonstrate that the thin film of GNPs on a glass/quartz surface can be successfully used as a refractive index (RI) sensor for different polar and nonpolar organic solvents. The as-formed GNP thin films on different surfaces show excellent catalytic activity in the borohydride reduction of p-nitrophenol.     

Photochemically-induced refractive index and fluoresence patterning on polymer films

The molecular design for large photo-induced refractive index changes in transparent visible light region was proposed and realized with norbornadiene polymers and poly(vinyl cinnamate). The patterning of pure refractive-index contract on their transparent films was made with near-field scanning optical microscopy (NSOM). Reversible fluorescence patterning on polymer films is also presented by using controlled energy transfer from a fluorescent pyromethene to a photochromic diarylethene.     

Control of refractive index of sol-gel tungsten oxide films

Tungsten oxide films were prepared by a complexing agent-assisted sol-gel process. All the films were at 500°C were crystalline and transparent. The refractive index n and extinction coefficient k of the films were calculated from the transmittance and reflectance spectra in the visible and infrared regions. The values of n were lowered to depend on the organic ligands used in the preparation of the sols. The use of such ligands may be a mean to control the refractive index of coatings.     

Kinetics of refractive index changes in polymeric photochromic films

Methacrylate copolymers containing, in side chain azobenzene groupings with heterocyclic sulfonamide substituents: N-(2,6-dimethylpyrimidin-4-yl)sulfamoyl (sulfisomidine) and N-(5-methylisoxazol-3-yl) sulfamoyl (sulfamethoxazole) were investigated. The materials undergo reversible trans-cis isomerisation during illumination with light. This results in changes of dipole moment, polarizability and refractive index. Ellipsometric measurements showed a distinct decreasing refractive index during illumination with light corresponding to absorption band (ca. 450 nm). Depending on the polymer, the change of real part of refractive index in spin-coated films was between 0.016 and 0.031. The dynamics of growth and decay of refractive index changes, was described by biexponential function approach.     

Refractive index modulation in polymeric photochromic films

Photochromic properties of methylacrylate monomers and polymers containing azobenzene groups with heterocyclic sulfonamide functionalities viz sulfisomidyne (4-amino-N-[2,6-dimethylpyrimidyn-4-yl]benzenesulfonamide) and sulfamethoxazole (4-amino-N-[5-methylisoxazol-3-yl]benzenesulfonamide) substituents were investigated. On illumination with light the azobenzene group underwent trans-cis isomerisation, which was manifested by a drop in the absorbance of the maximum absorption peak at ca. 450 nm and by decrease in refractive index. Quantum chemical calculations showed significant differences in UV-VIS spectra, dipole moments, polarizability and refractive index between both cis and trans form of the chromophoric monomers. The illumination of spin-coated polymer films during ellipsometry measurements resulted in a change in refractive index within the range of 0.014 to 0.025. The dynamics of growth and decay of refractive index changes, was described by biexponential functions approach.     

Rayleigh scattering study and particle density determination of a high refractive index TiO2 nanohybrid polymer

We have experimentally carried out a Rayleigh scattering study of a high refractive index TiO(2) nanohybrid polymer. By employing the Rayleigh scattering technique with at least three different wavelengths, we can obtain the Rayleigh ratio of the TiO(2) nanohybrid polymer at each utilized wavelength. These measured Rayleigh ratios are then used to estimate the size of the nanoparticle and determine the number of nanoparticles per unit volume or particle density. Furthermore, this technique can be used to evaluate the dominant size of nanoparticles in the nanohybrid polymer mainly contributed to Rayleigh scattering.     

Drying and nondrying layer-by-layer assembly for the fabrication of sodium silicate/TiO2 nanoparticle composite films

Influences of drying and nondrying steps on structures of layer-by-layer (LbL) assembled sodium silicate/TiO(2) nanoparticles films (donated as silicate/TiO(2) films) have been systematically investigated. The nondrying LbL assembly produces highly porous silicate/TiO(2) films with large thickness. In contrast, the silicate/TiO(2) films fabricated with a drying step after each layer deposition are flat and thin without porous structures. In situ atomic force microscopy (AFM) measurements confirm that the sodium silicate and TiO(2) nanoparticles are deposited in their aggregated forms. A N(2) drying step can disintegrate the aggregated silicate and TiO(2) nanoparticles to produce thin silicate/TiO(2) films with compact structures. Without the drying steps, the aggregated silicate and TiO(2) nanoparticles are well retained, and their LbL assembly produces highly porous silicate/TiO(2) films of large thickness. The highly porous silicate/TiO(2) films are demonstrated to be useful as reusable film adsorbents for dye removal from wastewater because they can adsorb a large amount of cationic organic dyes and decompose them under UV irradiation. The present study is meaningful for exploring drying/nondrying steps for tailoring structure and functions of LbL assembled films.     

On the complex refractive index of N-doped TiO2 nanospheres and nanowires in the terahertz spectral region

In this paper, the terahertz (THz) transmission measurement technique was applied to characterize titanium dioxide (TiO₂) nanospheres and nanowires subjected to thermal treatments under various conditions. Differences in the spectral features of the nanospheres and nanowires were observed due to treatment and annealing of the samples in different gas atmospheres. The observations made can be explained based on the formation of new phonon bands and/or widening of the phonon bands due to polymorphism. A singly subtractive Kramers Kronig dispersion relation was utilized to estimate the frequency-dependent real refractive index of the various samples, having a priori unknown sample thickness, from the absorbance data.     

Quantitative characterization of optical anisotropy in high refractive index films

Waveguide coupling measurements of polymers have largely concentrated on the application of mode analysis to the study of thin supported films (such as spin coatings). The use of prism coupling to study thick, freestanding polymer films, however, has not been reported. In this paper, the ability of prism coupling to characterize the three-dimensional optical properties of thick, freestanding polymer films and sheets is demonstrated. A modified prism coupling procedure is described that allows the determination of all three principal refractive indices in thick, three-dimensionally anisotropic freestanding films. A Metricon prism coupler is used in a manner similar to an Abbé refractometer for the measurement of isotactic polypropylene, poly(ethylene terephthalate), PMDA-ODA polyimide, and poly(phenylene sulfide). Three series of PMDA-ODA films are also investigated in this study. The first series has been drawn to different extensions from three-dimensionally random films. The second series has random orientation in the plane of the film but different degrees of planarity with respect to the through direction. The third series are commercial films of varying thickness. These three series of films are compared as to the optical an-isotropy that is developed from the three different fabrication processes. © 1993 John Wiley & Sons, Inc.     

Zinc(II) tetraarylporphyrins anchored to TiO2, ZnO, and ZrO2 nanoparticle films through rigid-rod linkers

A series of six Zn(II) tetraphenylporphyrins (ZnTPP), with a phenyl (P) or oligophenyleneethynylene (OPE = (PE) n ) rigid-rod bridge varying in length (9-30 A) and terminated with an isophthalic acid (Ipa) anchoring unit, were prepared as model dyes for the study of sensitization processes on metal oxide semiconductor nanoparticle surfaces (MO(n) = TiO(2), ZnO, and insulating ZrO(2)). The dyes were designed such that the electronic properties of the central porphyrin chromophore remained consistent throughout the series, with the rigid-rod anchoring unit allowing each porphyrin unit to be located at a fixed distance from the metal oxide nanoparticle surface. Electronic communication between the porphyrin and the rigid-rod unit was not desired. Rigid-rod porphyrins ZnTPP-Ipa, ZnTPP-P-Ipa, ZnTPP-PE-Ipa, ZnTPP-(PE)(2)-Ipa, ZnTPP-(PE)(3)-Ipa, and ZnTMP-Ipa (with mesityl substituents on the porphyrin ring) were synthesized using combinations of mixed aldehyde condensations and Pd-catalyzed cross-coupling reactions. Their properties, in solution and bound, were compared with that of Zn(II) 5,10,15,20-tetra(4-carboxyphenyl)porphyrin ( p-ZnTCPP) as the reference compound. Solution UV-vis and steady-state fluorescence spectra for all six rigid-rod-Ipa porphyrins were almost identical to each other and to that of p-ZnTCPP. Cyclic voltammetry and differential pulse voltammetry scans of the methyl ester derivatives of the six rigid-rod-Ipa porphyrins, recorded in dichloromethane/electrolyte, exhibited redox behavior typical of ZnTPP porphyrins, with the first oxidation in the range +0.99 to 1.09 V vs NHE. All six rigid-rod-Ipa porphyrins and p-ZnTCPP were bound to metal oxide (MO(n) = TiO(2), ZnO, and insulating ZrO(2)) nanoparticle films. The Fourier transform infrared attenuated total reflectance spectra of all compounds bound to MO n films showed a broad band at 1553-1560 cm(-1) assigned to the v(CO(2)(-)) asymmetric stretching mode. Splitting of the Soret band into two bands at 411 and 423 nm in the UV-vis spectra of the bound compounds, and broadening and convergence of both fluorescence emission bands in the fluorescence spectra of the porphyrins bound to insulating ZrO(2) were also observed. Such changes were less evident for ZnTMP-Ipa, which has mesityl substituents on the porphyrin ring to prevent aggregation. Steady-state fluorescence emission of rigid-rod-Ipa porphyrins bound to TiO(2) and ZnO through the longest bridges (>14 A) showed residual fluorescence emission, while fluorescence quenching was observed for the shortest compounds.     

Preparation of thin silica films with controlled thickness and tunable refractive index

Silica films with controlled thickness and refractive index have been formed by the sequential adsorption of a cationic polyelectrolyte and silica sols. The conditions used to prepare the sol were varied, and allowed films with refractive indices as low as 1.16 to be obtained. The sequential adsorption technique allows the thickness of these films to be controlled in increments of 5-10 nm, depending on the desired refractive index. Scanning electron microscopy revealed that a low packing density of constituent silica particles was responsible for the low indices of these films. The as-adsorbed films are thermally robust; calcination at 500 degrees C resulted in only very small decreases in film thickness (by < or =1.8%) and refractive index (to as low as 1.14). After calcination, the silica films remained hydrophilic and sorbed water vapor from the atmosphere. As a result, the refractive indices of these films increased with increasing relative humidity (RH). The dependence of the refractive index on RH was eliminated by treating the calcined films with trimethylchlorosilane.     

Solid-solid interface formation in TiO2 nanoparticle networks

Aiming at a comparison of microstructure and paramagnetic properties of mesoporous TiO(2) nanoparticle networks, we subjected entirely different TiO(2-x) precursor structures to vacuum annealing. The transformation of an amorphous TiO(2-x) gel--obtained by sol-gel processing of an ethylene glycol-modified titanium precursor--into a network of interconnected anatase nanocrystals was explored by means of X-ray diffraction, nitrogen sorption, and electron microscopy. Crystalline junctions between the particles emerge from temperature treatment. This process of particle network formation is different from that related to the vapor phase grown anatase nanocrystals where particle-particle interface formation is induced by contact with water. It was found that, after annealing up to 873 K and controlled sample purification in oxygen atmosphere, both types of samples exhibit high concentrations of particle-particle interfaces and comparable properties in terms of surface area, porosity, and microstructure. With electron paramagnetic resonance (EPR) we observed on nonstoichiometric TiO(2-x) networks an identical type of subsurface defect which is related to the presence of solid-solid interfaces.     

Photoinduced electron transfer between a carotenoid and TiO2 nanoparticle

The dynamics of photoinduced electron injection and recombination between all-trans-8'-apo-beta-caroten-8'-oic acid (ACOA) and a TiO(2) colloidal nanoparticle have been studied by means of transient absorption spectroscopy. We observed an ultrafast ( approximately 360 fs) electron injection from the initially excited S(2) state of ACOA into the TiO(2) conduction band with a quantum yield of approximately 40%. As a result, the ACOA(*)(+) radical cation was formed, as demonstrated by its intense absorption band centered at 840 nm. Because of the competing S(2)-S(1) internal conversion, approximately 60% of the S(2)-state population relaxes to the S(1) state. Although the S(1) state is thermodynamically favorable to donate electrons to the TiO(2), no evidence was found for electron injection from the ACOA S(1) state, most likely as a result of a complicated electronic nature of the S(1) state, which decays with a approximately 18 ps time constant to the ground state. The charge recombination between the injected electrons and the ACOA(*)(+) was found to be a highly nonexponential process extending from picoseconds to microseconds. Besides the usual pathway of charge recombination forming the ACOA ground state, about half of the ACOA(*)(+) recombines via the ACOA triplet state, which was monitored by its absorption band at 530 nm. This second channel of recombination proceeds on the nanosecond time scale, and the formed triplet state decays to the ground state with a lifetime of approximately 7.3 micros. By examination of the process of photoinduced electron transfer in a carotenoid-semiconductor system, the results provide an insight into the photophysical properties of carotenoids, as well as evidence that the interfacial electron injection occurs from the initially populated excited state prior to electronic and nuclear relaxation of the carotenoid molecule.     

Measurements and modeling of recombination from nanoparticle TiO2 electrodes

Electron-transfer reactions from nanoparticle TiO(2) films to outer-sphere redox shuttles were investigated. Steady-state dark current density versus applied potential and open circuit voltage decay measurements were employed to determine the rates of recombination to cobalt(III) tris(4,4'-dimethyl-2,2'-bipyridyl), [Co(Me(2)bpy)(3)](3+), and ruthenium(III) bis(2,2'-bipyridyl)-bis(N-methylimidozole), [Ru(bpy)(2)(MeIm)(2)](3+). A striking difference in the magnitude as well as the shape of the electron lifetimes for TiO(2) electrodes in contact with these two redox shuttles is observed. A model based on Marcus theory is developed to describe recombination, including contributions from conduction band electrons and surface states. Excellent agreement was found between the modeled and measured lifetimes. The model allows for identification of each contributing component of electron transfer to the measured lifetimes. Comparison of the different components of the modeled lifetimes to the measured lifetimes provides clear evidence for recombination mediated through surface states.     

Cyclic allylic sulfide based photopolymer for holographic recording showing high refractive index modulation

The development and characterization of a new holographic photopolymer system showing high refractive index modulation (∆n) is presented. It exploits the ring-opening polymerization reaction of a cyclic allylic sulfide (CAS) monomer, which is dispersed in a cellulose acetate butyrate (CAB) polymer matrix together with a blue sensitive radical photoinitiator. Volume Phase Holographic Gratings (VPHGs) obtained using these films show a very good fidelity of the transferred pattern, without deviations from the theoretical curves. A high ∆n is obtained due to the addition to this system of a tetrafunctional thiol crosslinker, which maximizes the material potential (formula limit) of the formulation. It also allows for a thermal post process of the gratings, further enhancing the ∆n. The photopolymer properties are evaluated as function of the monomer and thiol concentration to determine the optimal composition, at which a ∆n greater than 0.03 is obtained. This is a considerably high value in the field of photopolymers for holography and it enables the manufacturing of efficient holograms.     

Induced refractive index in thin films of polymeric organosilanes under UV irradiation

Changes in the refractive indices of thin films of three polymeric organosilanes at wavelengths of 400-1500 nm, occurring under UV radiation, were examined.     

Morphological and photoelectrochemical characterization of core-shell nanoparticle films for dye-sensitized solar cells: Zn-O type shell on SnO2 and TiO2 cores

Core-shell type nanoparticles with SnO2 and TiO2 cores and zinc oxide shells were prepared and characterized by surface sensitive techniques. The influence of the structure of the ZnO shell and the morphology ofnanoparticle films on the performance was evaluated. X-ray absorption near-edge structure and extended X-ray absorption fine structure studies show the presence of thin ZnO-like shells around the nanoparticles at low Zn levels. In the case of SnO2 cores, ZnO nanocrystals are formed at high Zn/Sn ratios (ca. 0.5). Scanning electron microscopy studies show that Zn modification of SnO2 nanoparticles changes the film morphology from a compact mesoporous structure to a less dense macroporous structure. In contrast, Zn modification of TiO2 nanoparticles has no apparent influence on film morphology. For SnO2 cores, adding ZnO improves the solar cell efficiency by increasing light scattering and dye uptake and decreasing recombination. In contrast, adding a ZnO shell to the TiO2 core decreases the cell efficiency, largely owing to a loss of photocurrent resulting from slow electron transport associated with the buildup of the ZnO surface layer.