Light induced gradient refractive index materials

Controlled and patterned variation of refractive index (wavefront) across a lens surface was obtained via the use of “phase mask”. Gradient interpenetrating network was selected to screen the acrylate and epoxy monomer to obtain necessary refractive index change over the lens surface. The best photoinitiator system was determined to give a stable and transparent wavefront as a mixture of 2 wt% Irgacure 250 (I 250), 1 wt% Isopropylthoxanthone (ITX) and 0.5 wt Irgacure 184 (I 184). It is found that a dipropylene glycol diacrylate (SR 508) and a triethylene glycol dimethacrylate (TGDM) improved the stability of the transparent wavefront because of higher Tg of the network. Haze problem, a consequence of diffusion of one monomer to other network because of the rate differences, was eliminated with IPN composed of TGDM (an acrylate with slow polymerization rate) and bis (3,4‐epoxy cyclohexylmethyl)adipate (BECMA, an epoxy with fast polymerization rate). A high refractive index additive, bromonaphthalene, resulted the best wavefront with lens power when incorporated into BECMA and TGDM IPN. Copyright © 2015 John Wiley & Sons, Ltd.     

Alternating copolymerization of bis(hexafluoroisopropyl) fumarate with styrene and vinyl pentafluorobenzoate: Transparent and low refractive index polymers

Bis(hexafluoroisopropyl) fumarate (BHFIPF) did not homopolymerize with free radical initiators. However, BHFIPF yielded alternating copolymers with styrene in bulk with Azobisisobutyronitrile (AIBN) as a radical initiator. The monomer reactivity ratios of BHFIPF (M₁) and styrene (M₂) were calculated as r₁ = 0.00 and r₂ = 0.02. BHFIPF also copolymerized with vinyl pentafluorobenzoate (VPFB) in bulk and in pentafluoroisopropanol solution to produce an alternating copolymer. The reactivity ratios of BHFIPF (M₁) with VPFB (M₂) were r₁ = 0.00 and r₂ = 0.05 in bulk and r₁ = 0.01 and r₂ = 0.11 in pentafluoroisopropanol, respectively. The glass transition temperatures (T_g) of the BHFIPF‐styrene and BHFIPF‐VPFB copolymers were 107 and 86 °C, respectively. The BHFIPF‐styrene copolymer was thermally stable, and the thermal degradation temperature (T_d) was 400 °C, whereas the T_d of BHFIPF‐VPFB copolymer was 240 °C. The films obtained by casting from tetrahydrofuran (THF) solutions of these copolymers were flexible and transparent. Their refractive indices were 1.4048 for the BHFIPF‐styrene copolymer, and 1.3980 for the BHFIPF‐VPFB copolymer at 633 nm, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

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.     

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.     

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.     

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.     

UV‐induced refractive index modulation of photoreactive polymers bearing N‐acylcarbazole groups

In this study, we report on the synthesis and characterization of photoreactive polymers bearing N‐acetylcarbazole and N‐formylcarbazole groups, respectively. These polymers were easily accessible by polymer analogous acylation of commercially available poly‐(2‐vinylcarbazole). While poly(1‐(2‐vinyl‐9H‐carbazol‐9‐yl)ethanone) (poly‐ 1 ) undergoes a partial photochemical Fries rearrangement, poly(2‐vinyl‐9H‐carbazole‐9‐carbaldehyde) (poly‐ 2 ) decarbonylates smoothly when exposed to UV irradiation. The difference in reactivity between the two acylated polymers is because of the lower stability of the formyl radical, which is formed in the first stage of this photoreaction. Ellipsometric measurements of thin films showed that the photo‐Fries rearrangement in poly‐ 1 causes a change in refractive index by Δn = +0.01 at 650 nm. UV illumination of poly‐ 2 results in a change of the refractive index by Δn = +0.03 at 650 nm, which can be explained by the high yield of the photodecarbonylation of the N‐formylcarbazole groups. Refractive index patterns can be easily realized using lithographic techniques as demonstrated by optical microscopy using a phase contrast set‐up for visualization. Patterned films of poly‐ 1 and poly‐ 2 with feature sizes of about 5 μm were obtained with a mask aligner. Photoreactive polymers bearing N‐acylcarbazole groups are of potential interest for optical applications such as waveguides, optical switches, and data storage devices. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Modeling of X-ray-induced refractive index changes in poly(methyl methacrylate).

The refractive index of bulk poly(methyl methacrylate) samples is modified by X-ray exposure. The intensity of the radiation is distributed over an energy range of 1 to 20 keV with a maximum at 3 keV. For an absorbed dose of about 1 kJ cm(-3), an increase of the refractive index of up to 3x10(-4) is observed. However, for much lower doses of about 10 J cm(-3) a decrease of 4x10(-4) appears. These refractive index changes, as well as the simultaneously arising radiation-induced thickness changes, are detected interferometrically. Based on these observations, on dose calculations, and on literature data, a model is proposed which describes quantitatively the observed refractive index changes. The refractive index increase is caused by a radiation-induced chemical alteration of the polymer composition, while the refractive index decrease is correlated with a decrease of mass density.     

High refractive index adamantane‐based silicone resins for the encapsulation of light‐emitting diodes

The encapsulation of high power light emitting diode (LED) needs the silicone resins to have relative high refractive index and thermal‐aging properties. Herein, high refractive index adamantane‐based phenyl epoxy‐silicone (APES) resins for LED encapsulation were synthesized by the sol‐gel condensation of 1‐adamantane methanol propyltrimethoxysilane‐3‐urethane, γ‐(2,3‐epoxypropoxy)propytrimethoxysilane and diphenylsilanediol. These adamantane‐based silicone resins have multifunctional groups including adamantyl group, phenyl group, and epoxy group in order to meet the various requirements for LED encapsulation. Importantly, the adamantane group in the silicone resins benefits for high refractive index and anti‐thermal properties. These APES resins were characterized by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. When APES resins were cured by methylhexahydrophthalic anhydride, they showed relatively high refractive index of 1.56, high hardness, and high thermal resistance. The encapsulated LED demonstrated high adhesion properties by red‐ink tests. These merits make adamantane‐based silicone resins promising candidates as LED encapsulation materials.     

Simultaneous analysis of esters and acylglycerols in biodiesel by high-performance liquid chromatography with refractive index detection

Currently, gas chromatography (GC) is the most widely used analytical technique to verify the quality of biodiesel in relation to its glyceride and fatty acid methyl ester (FAME) contents, even though its use has some disadvantages, such as damage to the injector and column caused by the presence of trace levels of triacylglycerols in biodiesel, which means the column has to be replaced every 3 months; the need for the sample to be derivatized, which, while improving chromatographic separation, also increases analysis time; and the use of several imported standard solutions. The main aim of this work was to use high-performance liquid chromatography with refractive index detection (HPLC-RI) to simultaneously quantify the glyceride (mono, di, and triacylglycerol) and FAME contents of biodiesel. The proposed method showed satisfactory results when compared with those obtained by the reference method (GC), particularly when these results were within the working ranges of the reference method. The proposed method using HPLC-RI is therefore promising and could potentially be used instead of the reference method, since the results it yielded were statistically equivalent, with 95% confidence, to the results obtained by the reference method (GC) for the nine samples of commercial biodiesel analyzed in this study.     

One‐pot synthesis of polymer/inorganic hybrids: toward readily accessible,low‐loss,and highly tunable refractive index materials and patterns

The realization that modulated light pulses can be transported in a confined fashion over long distances within a structure that comprises a controlled spatial distribution of the refractive index n—as in optical fibres and waveguides—has, without doubt, underpinned the telecommunications revolution witnessed during the 20th century. The refractive index n, quantifying how light propagates in a given medium, as a consequence, has become one of the most important materials properties in designing photonics products. The other key characteristic for most optical and photonic applications is the amount of light that is absorbed by a material, expressed as the extinction coefficient κ. Although a range of organic/inorganic hybrid materials have been advanced with tunable refractive index, only a few systems combine a high n, sufficiently low κ and straightforward sample preparation to allow simple fabrication of highly transparent, low‐loss structures. Here, we present a hybrid material that can be readily produced in water via a one‐pot synthesis directly from commercially available, low‐cost precursors. Moreover, our hybrid material can be solution‐processed, yielding systems of an extinction coefficient <0.01, and a refractive index, which can be controlled to adopt values between 1.5 to at least 2.1. Unprecedentedly, simple post‐deposition procedures such as thermal annealing or irradiation with high‐intensity UV‐light allow adjusting n also after film fabrication, offering an exceptional degree of freedom in designing and tailoring also more complex photonic architectures or planar wave‐guides, for example, through creation of in‐plane refractive index patterns. As a proof‐of‐concept, we demonstrate fabrication of waveguides based on local heating. The versatility of our materials is further illustrated by the production of lenses and dielectric filters of ～100% reflectivity in a given wavelength regime. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 000: 000–000, 2011     

Flexible nanocrystalline‐titania/polyimide hybrids with high refractive index and excellent thermal dimensional stability

In this study, a novel synthetic route was developed to prepare polyimide–nanocrystalline–titania hybrid optical films with a relatively high titania content (up to 50 wt %) and thickness (20–30 μm) from soluble polyimides containing hydroxyl groups. Two series of newly soluble polyimides were synthesized from the hydroxy‐substituted diamines with various commercial tetracarboxylic dianhydrides. The hydroxyl groups on the backbone of the polyimides could provide the organic–inorganic bonding and resulted in homogeneous hybrid solutions by controlling the mole ratio of titanium butoxide/hydroxyl group. AFM, SEM, TEM, and XRD results indicated the formation of well‐dispersed nanocrystalline‐titania. The flexible hybrid films could be successfully obtained and revealed relatively good surface planarity, thermal dimensional stability, tunable refractive index, and high optical transparency. A three‐layer antireflection coating based on the hybrid films was prepared and showed a reflectance of less than 0.5% in the visible range indicated its potential optical applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1433–1440, 2010     

Thermally induced changes in amorphous indium-tin-oxide thin films

Amorphous indium-tin-oxide (ITO) transparent conducting film (15 at% Sn; thickness, 150–190 nm) was deposited on silicon wafer at room temperature by RF magnetron sputtering for temperature programmed desorption (TPD) in vacuum. The thermal crystallization was accompanied by evolution of water vapor (the main gas), argon and carbon dioxide. The total amount of evolved water vapor (H₂O [mol]/(In [mol]+Sn [mol])>0.2) was one or two orders of magnitude more than that from the nanocrystalline ITO films reported in our previous papers. The thermal change of amorphous ITO film was remarkably affected by the position of the substrate. An abrupt gas evolution was characteristic of the amorphous ITO films deposited on the position near the target center. The evolution temperature (548–563 K) was higher than the gas evolution temperature from the crystalline films. The far from center positioned films crystallized at higher temperature with relatively slower evolution of the gases.     

Viscosity and refractive index adjustment of poly(methyl methacrylate‐co‐ethyleneglycol dimethacrylate) for application in microoptics

Polymer optical components like waveguides or lenses are gaining more and importance as passive or active devices enabling the formation of a sensor and detector platform, e.g. for monitoring the health of large area functional surfaces, which are difficult to access like the wings of an off‐shore wind energy plant. With respect to low‐loss waveguiding and the use of chemical and mechanical stable polymers there is a need to tailor the optical as well as the thermomechanical properties. The given approach describes the addition of electron‐rich small organic molecules like phenanthrene to a poly(methyl methacrylate)‐based polymer matrix enabling a significant refractive index increase from 1.49 up to almost 1.55 (@589 nm). As undesirable side effects the optical transmittance in the visible range at higher guest molecule content is reduced, and a pronounced plasticizing occurs. Both hamper the application of the mixture, e.g. as optical waveguide material. The plasticizing and the accompanied drop of the glass transition temperature, determining the maximum operation temperature, can be partially compensated by the copolymerization of the methyl methacrylate monomer (MMA) with the difunctional monomer ethyleneglycol dimethacrylate (EGDMA) at certain crosslinker content. The resulting new developed guest–host mixtures enable the realization of optical devices with adjusted rheological behavior prior to curing and tailored optical properties after polymerization. Copyright © 2015 John Wiley & Sons, Ltd.     

Reactions of titanium alkoxide with SiH containing polymers as a route to titanium/siloxane hybrid materials with enhanced refractive index

Reactions of titanium tetrabutoxide with polyhydromethylsiloxane (PHMS) and with some hydromethylsiloxane copolymers were used for synthesis of light transparent materials having enhanced refractive index. The FTIR, ¹H NMR and ²⁹Si NMR spectroscopies were used to study the reaction between PHMS and titanium tetrabutoxide in toluene. Reaction of SiH functional siloxane polymers with titanium tetrabutoxide results in a titanium-containing heterosiloxane prepolymers that are stable under anhydrous anaerobic conditions. Exposure of the resulting materials to humid air transforms them into light transparent titanium/siloxane nanocomposites with enhanced refractive index. The films of these composites formed during the spin-coating process were characterized by UV–Vis, ellipsometry, IR and ²⁹Si NMR spectroscopies and transmission electron microscopy (TEM). Titanium/siloxane hybrid films obtained on the basis of poly(phenylmethylsiloxane-co-hydromethylsiloxane) copolymer are free of cracks and have a refractive index of up to 1.60.     

Selective solvent annealing induced phase separation and dewetting in PMMA/SAN blend ultrathin films

Phase behaviors induced by solvent annealing in poly(methyl methacrylate) (PMMA) and poly(styrene‐ran‐acrylonitrile) (SAN) blend ultrathin films have been investigated by atomic force microscopy and grazing incidence small‐angle X‐ray scattering. Our results indicate that both the phase separation within the blend and the dewetting of the film induced by composition fluctuation take place upon the selective solvent annealing, producing complex structures containing upper droplets (of one phase) and mimic‐films (of the other rich‐phase). The use of acetic acid (the selective solvent for PMMA) generates PMMA mimic‐film and SAN droplets, while the introduction of DMF (exhibiting better solubility for SAN) vapor results in the formation of SAN mimic‐film and PMMA droplets. Essentially, the interaction at polymer/substrate interface, resultant wettability of selected component, solubility of PMMA and SAN in adopted solvent dominate not only the phase separation and the dewetting of the whole film but also the synergism of them. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1243–1251     

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.     

Application of refractive index mixing rules in binary systems of hexadecane and heptadecane with n -alkanols at different temperatures

Density and refractive index have been experimentally determined for binary liquid mixtures of hexadecane and heptadecane with 1-butanol, 1-pentanol, 1-hexanol and 1-heptanol at 298.15, 308.15 and 318.15 K. A comparative study of Lorentz—Lorenz (L-L), Weiner (W) and Heller (H), and Gladstone-Dale (G-D) relations for predicting the refractive index of a liquid has been carried out to test their validity for the eight binaries over the entire mole fraction range of hexadecane and heptadecane at the three temperatures. Comparison of various mixing rules has been expressed in terms of average percentage deviation. The performance of the Lorentz-Lorenz and Heller relations is relatively better than that of the Weiner and Gladstone-Dale relations.     

Refractive index variation in nonaqueous sterically stabilized copolymer particles

We present procedures for preparing sterically stabilized polymer particles whose refractive index can be controlled over a range of a few percent. Particle sphericity and size distribution are such that suspensions crystallize at high concentrations. This at least ensures that Brownian motion dominates over particle settling and that the polydispersity is no more than about 10%. Of particular interest are new particles comprising poly(methylmethacrylate-co-trifluoroethylacrylate) that can be optically matched in single solvent, namely cis-decalin.