Multifunctional Optical Device with a Continuous Tunability over 500 nm Spectral Range Using Polymerized Cholesteric Liquid Crystals.

We report that polymerization makes a robust, practically applicable multifunctional optical device with a continuous wavelength tunable over 500 nm spectral range using UV-polymerizable cholesteric liquid crystals (CLCs). It can be used as a circular polarizer generating an extremely high degree of circularly polarized light with |g| = 1.85~2.00. It can also be used for optical notch filters, bandwidth-variable (from ~28 nm to ~93 nm) bandpass filters, mirrors, and intensity-variable beam splitters. Furthermore, this CLC device shows excellent stability owing to the polymerization of CLC cells. Its performance remains constant for a long time (~2 years) after a high-temperature exposure (170 °C for 1 h) and an extremely high laser beam intensity exposure (~143 W/cm2 of CW 532 nm diode laser and ~2.98 MW/cm2 of Nd: YAG pulse laser operation for two hours, respectively). The optical properties of polymerized CLC were theoretically analyzed by Berreman's 4 × 4 matrix method. The characteristics of this device were significantly improved by introducing an anti-reflection layer on the device. This wavelength-tunable and multifunctional device could dramatically increase optical research efficiency in various spectroscopic works. It could be applied to many instruments using visible and near-infrared wavelengths.

Continuously tunable optical notch filter and band-pass filter systems that cover the visible to near-infrared spectral ranges.

Spatially continuous tunable optical notch and band-pass filter systems that cover the visible (VIS) and near-infrared (NIR) spectral ranges from ∼460 nm to ∼1,000 nm are realized by combining left- and right-handed circular cholesteric liquid crystal (CLC) wedge cells with continuous pitch gradient. The notch filter system is polarization independent in all of the spectral ranges. The band-pass filter system, when the left- and right-handed CLCs are arranged in a row, is polarization independent, while when they are arranged at right angles, they are polarization dependent; furthermore, the full-width at half-maximum of the band-pass filter can be changed reversibly from the original bandwidth of 36 nm to 16 nm. Depending on the CLC materials, this strategy could be applied to the UV, VIS, and IR spectral ranges. Due to the high performance in the broad spectral range, cost-effective facile fabrication process, simple mechanical control, and small size, it is expected that our optical tunable filter strategies could become one of the key parts of laser-based Raman spectroscopy, fluorescence, life science devices, optical communication systems, astronomical telescopes, and so forth.

Active thermal fine laser tuning in a broad spectral range and optical properties of cholesteric liquid crystal.

In this study, we achieved active fine laser tuning in a broad spectral range with dye-doped cholesteric liquid crystal wedge-type cells through temperature control. The spatial pitch gradient of each position of the wedge cell at room temperature was almost maintained after developing a temperature gradient. To achieve the maximum tuning range, the chiral dopant concentration, thickness, thickness gradient, and temperature gradient on the wedge cell should be matched properly. In order to understand the laser tuning mechanism for temperature change, we studied the temperature dependence of optical properties of the photonic bandgap of cholesteric liquid crystals. In our cholesteric liquid crystal samples, when temperature was increased, photonic bandgaps were shifted toward blue, while the width of the photonic bandgap was decreased, regardless of whether the helicity was left-handed or right-handed. This is mainly due to the combination of decreased refractive indices, higher molecular anisotropy of chiral molecules, and increased chiral molecular solubility. We envisage that this kind of study will prove useful in the development of practical active tunable CLC laser devices.

Firsthand in situ observation of active fine laser tuning by combining a temperature gradient and a CLC wedge cell structure.

In situ direct observation of the lasing process in a cholesteric liquid crystal (CLC) laser array using a CMOS camera was used to investigate discontinuous laser tuning in a parallel CLC cell. In accordance with the discontinuous pitch change by thermal energy transfer, at the same time the laser wavelength undergoes an immediate and discontinuous shift. And we found out the reason why the CLC phase has domain textures. And this work develops a simple active tunable laser array by forming a spatial temperature gradient along a wedge CLC cell. With this new strategy, only just about 7 nm laser tuning range at room temperature is extremely widened over the 105 nm wavelength range with about 0.2 nm tuning resolution. Furthermore, there is no aging effect because the employed CLC array has only one chiral molecular concentration. This strategy could be used in a practical CLC laser device application.

Octupolar molecules for nonlinear optics: from molecular design to crystals and films with large second-harmonic generation.

We summarize the nonlinear optical (NLO) properties of octupolar molecules, crystals, and films developed in our laboratory. We present the design strategy, structure-property relationship, and second-order NLO properties of 1,3,5-trinitro- and 1,3,5-tricyano-2,4,6-tris(p-diethylaminostyryl)benzene (TTB) derivatives, TTB crystals, and films prepared by free-casting TTB in poly(methyl methacrylate) (PMMA). The first hyperpolarizability of TTB was fivefold larger than that of the dipolar analogue. Moreover, the TTB crystal showed unprecedentedly large second-harmonic generation (SHG). While TTB crystal films (20 wt% TTB/PMMA) on various substrates showed appreciable SHG values, the cylinder film exhibited much larger SHG values and large electro-optic (EO) coefficients. The large SHG values and EO coefficients, as well as the high thermal stability of the cylinder film, will make it a potential candidate for NLO device applications.

Optical Properties of Laser Lines and Fluorescent Spectrum in Cholesteric Liquid Crystal Laser.

We experimentally studied the comprehensive optical properties of the laser lines and fluorescent spectrum generated by a continuous tunable cholesteric liquid crystal (CLC) laser array. We found that the laser lines generated from a CLC with a right-handed circular helix were right-handed circular polarized and laser lines generated from a CLC with a left-handed circular helix were left-handed circular polarized. Inside the photonic band gap, the CLC structure with right-(left-) handed helicity suppressed the fluorescence generated with right (left) circular polarized light, and instead the suppressed right (left) circular polarized light energy moved to the outside of the photonic band gap, so we can say that the fluorescence intensity outside of the photonic band gap is enhanced with right (left) handed circular polarized light. Depending on the position of the photonic band gap, the fluorescence quantum yield value increased by up to ~15%. These enhanced fluorescence intensities at the PBG edge will evolve into lasing at the upper lasing threshold. It is particularly interesting to see that the fluorescence intensity and shape could be controlled by adjusting the external geometrical factor of the photonic band gaps. The lasing threshold of the CLC lasers was in the range of 1.5-5.3 µJ/pulse. For CLC laser device applications, it is necessary and essential to know the optical properties of the generated laser lines and of the fluorescence spectrum.

Temporal, thermal, and light stability of continuously tunable cholesteric liquid crystal laser array.

Fine-structured polymerized cholesteric liquid crystal (PCLC) wedge laser devices have been realized, with high fine spatial tunability of the lasing wavelength. With resolution less than 0.3 nm in a broad spectral range, more than one hundred laser lines could be obtained in a PCLC cell without extra devices. For practical device application, we studied the stability of the device in detail over time, and in response to strong external light sources, and thermal perturbation. The PCLC wedge cells had good temporal stability for 1 year and showed good stability for strong perturbations, with the lasing wavelength shifting less than 1 nm, while the laser peak intensities decreased by up to 34%, and the high energy band edge of the photonic band gap (PBG) was red shifted 3 nm by temperature perturbation. However, when we consider the entire lasing spectrum for the PCLC cell, the 1-nm wavelength shift may not matter. Although the laser peak intensities were decreased by up to 34% in total for all of the perturbation cases, the remaining 34% laser peak intensity is considerable extent to make use. This good stability of the PCLC laser device is due to the polymerization of the CLC by UV curing. This study will be helpful for practical CLC laser device development.

Continuous spatial tuning of laser emissions in a full visible spectral range.

In order to achieve a continuous tuning of laser emission, the authors designed and fabricated three types of cholesteric liquid crystal cells with pitch gradient, a wedge cell with positive slope, a wedge cell with negative slope, and a parallel cell. The length of the cholesteric liquid crystal pitch could be elongated up to 10 nm, allowing the lasing behavior of continuous or discontinuous spatial tuning determined by the boundary conditions of the cholesteric liquid crystal cell. In the wedge cell with positive slope, the authors demonstrated a continuous spatial laser tuning in the near full visible spectral range, with a tuning resolution less than 1 nm by pumping with only a single 355 nm laser beam. This continuous tuning behavior is due to the fact that the concentration of pitch gradient matches the fixed helical pitch determined by the cell thickness. This characteristic continuous spatial laser tuning could be confirmed again by pumping with a 532 nm laser beam, over 90 nm in the visible spectral range. The scheme of the spatial laser tuning in the wedge cell bearing a pitch gradient enabled a route to designing small-sized optical devices that allow for a wide tunability of single-mode laser emissions.

Electro-optic effect in crystalline films of transverse planar octupolar symmetry.

We present theoretical and experimental demonstrations of the electro-optic activity in crystalline molecular thin films with octupolar D(3h) symmetry. Applying a longitudinal electric field modulation within the molecular plane, we analyze the induced refractive index change relative to the orientation of the octupoles in their plane, and show that a maximum value is reached when one octupolar branch lies along the direction of the modulating field. These characteristics, as well as their electric field dependence, are drastically different from more traditional one-dimensional symmetry samples, bringing additional advantages related to electro-optic coupling possibilities.

Continuous spatial tuning of laser emissions with tuning resolution less than 1 nm in a wedge cell of dye-doped cholesteric liquid crystals.

We report the design and fabrication of a wedge structured CLC film incorporating a spatial gradient of a chiral dopant concentration. A continuous spatial laser tuning in the broad visible spectral range with tuning resolution less than 1 nm is demonstrated, which renders a CLC-based micron-sized laser an important continuously tunable laser device.

Photoluminescence characteristics for hybrid nanotubes of light emitting poly(3-methylthiophene) coated with copper: fluorescence effect.

The enhanced nanometer-scale photoluminescence (PL) and quantum yield of hybrid double layered nanotubes (HDLNTs) consisting of a light-emitting poly(3-methylthiophene) (P3MT) nanotube coated with nanometer-scale copper (Cu) metal were observed and presented. The HDLNTs of the Cu coated P3MT (P3MT/Cu) were synthesized through a sequential electrochemical synthetic method in an anodic alumina oxide (Al2O3) nanoporous template. We confirmed that the Cu nanotubes were covered outside the light emitting P3MT nanotubes based a high resolution transmission electron microscope image. From laser confocal microscope (LCM) PL experiments of an isolated single strand of the P3MT nanotubes and of their HDLNTs, we observed a -100 times enhancement of the PL peak intensity for the HDLNTs of P3MT/Cu compared to that of the P3MT single nanotube, which was qualitatively confirmed through the measurement of the quantum yield. The energy and/or charge transfer effects in surface plasmon resonance contributed to the larger enhancement of the PL efficiency of the hybrid P3MT/Cu nanotubes. The PL decay life-time of the excitons of the P3MT nanotubes using a time resolved PL was not changed after the formation of the HDLNTs, implying that the PL enhancement of the hybrid nanotubes might have originated from fluorescence, not phosphorescence.

First hyperpolarizabilities of 1,3,5-tricyanobenzene derivatives: origin of larger beta values for the octupoles than for the dipoles.

A series of donor-acceptor substituted stilbene and diphenylacetylene derivatives and their octupolar analogues have been synthesized and the linear and nonlinear optical properties (beta) studied by both experiments and theoretical calculation. The lambda(max) of the dipoles increases with the conjugation length and is always larger when the C=C bond is used, instead of the C[triple bond]C bond, as the conjugation bridge. Although the lambda(max) values of the octupoles show no clear trend, they are much larger than those of the dipoles. The beta(0) values of the dipoles increase with conjugation length and as the conjugation bridge is changed from the C[triple bond]C to C=C bond. This increase is accompanied by an increase in either lambda(max) or the oscillator strength. Similarly, the beta(0) values of the octupoles increase with the conjugation length and with a change in the donor in the order: NEt2 < N(i-amyl)Ph < NPh2. Moreover, beta(yyy)/beta(zzz) ratios are in the range of 1.6-3.9 and decrease with the conjugation length. Beta values calculated by the finite-field and sum-over-states methods are in good agreement with the experimental data. Also, there is a parallel relationship between the calculated beta values and bond length alternation (BLA). From these results, the origin of the larger beta values for octupoles than for dipoles is assessed.

Two-photon absorption properties of 2,6-bis(styryl)anthracene derivatives: effects of donor-acceptor substituents and the pi center.

A series of 2,6- and 2,7-bis(styryl)anthracene derivatives with the donors at the styryl group and acceptors at the 9,10-positions have been synthesized, and their two-photon cross sections (Phidelta(max)) were determined. These compounds exhibit a peak two-photon absorptivity (delta(max)) in the range of 700-2500 GM at 780-1030 nm. Values of lambda(max) and Stokes shifts increase as the acceptor is changed to a stronger one. There is also a parallel increase in lambda(2)max and delta(max) with the same variation of the chromophore structure. Both lambda (2)(max)and Phidelta(max) have been optimized by introducing donor-substituted styryl groups at the 2,6-positions and p-cyanophenyl groups at the 9,10-positions, respectively. The effect of a pi center on the two-photon absorption properties has been assessed by comparing the existing data for a variety of D-pi-D derivatives.

Two-photon sensor for metal ions derived from azacrown ether.

A two-photon sensor for the metal ions derived from azacrown ether as the receptor is reported. The sensor emits strong two-photon fluorescence when excited by 800 nm laser photons. Moreover, the binding constants measured by the one- and two-photon fluorescence are similar. This result may be useful for the design of efficient two-photon fluorescence probes for biological substrates.

Triphenylamine derivatives with large two-photon cross-sections.

[structure: see text] Triphenylamine derivatives have been synthesized and shown to exhibit large two-photon cross-sections at a wide range of wavelengths and the largest value measured by fs Z-scan experiment. Moreover, a linear relationship is noted between the two-photon cross-sections measured by ns fluorescence and fs Z-scan methods.

2,6-Bis(styryl)anthracene derivatives with large two-photon cross-sections.

The first synthesis of 2,6-bis(styryl)anthrance derivatives with very large two-photon cross sections is reported.

Bis-1,4-(p-diarylaminostryl)-2,5-dicyanobenzene derivatives with large two-photon absorption cross-sections.

Synthesis and physical properties of novel multibranched two-photon materials are reported. The compound with three units of 4-(p-diphenylaminostyryl)-2,5-dicyanostyryl moieties attached to the central triphenylamine core exhibits a very large two-photon absorption cross-section.