Beam shaping diffractive wave plates [Invited].

We present and discuss opportunities opened up by a new generation of beam shaping optical elements that combine capabilities of digital spatial light polarization converters and diffractive properties of thin liquid crystalline films with patterned orientation of anisotropy axis (diffractive wave plates). Several functions of the new generation beam shapers are demonstrated, among them converting a laser beam of a Gaussian profile into a ring profile in the far field, a flattop profile, and into complex images. We also describe electrically controlled beam shaping optical elements which can be turned off and on within milliseconds by applying a low external voltage. Optical, morphological, and electro-optical properties of the components are characterized.

Digital polarization holography advancing geometrical phase optics.

Geometrical phase or the fourth generation (4G) optics enables realization of optical components (lenses, prisms, gratings, spiral phase plates, etc.) by patterning the optical axis orientation in the plane of thin anisotropic films. Such components exhibit near 100% diffraction efficiency over a broadband of wavelengths. The films are obtained by coating liquid crystalline (LC) materials over substrates with patterned alignment conditions. Photo-anisotropic materials are used for producing desired alignment conditions at the substrate surface. We present and discuss here an opportunity of producing the widest variety of "free-form" 4G optical components with arbitrary spatial patterns of the optical anisotropy axis orientation with the aid of a digital spatial light polarization converter (DSLPC). The DSLPC is based on a reflective, high resolution spatial light modulator (SLM) combined with an "ad hoc" optical setup. The most attractive feature of the use of a DSLPC for photoalignment of nanometer thin photo-anisotropic coatings is that the orientation of the alignment layer, and therefore of the fabricated LC or LC polymer (LCP) components can be specified on a pixel-by-pixel basis with high spatial resolution. By varying the optical magnification or de-magnification the spatial resolution of the photoaligned layer can be adjusted to an optimum for each application. With a simple "click" it is possible to record different optical components as well as arbitrary patterns ranging from lenses to invisible labels and other transparent labels that reveal different images depending on the side from which they are viewed.

Broadband waveplate lenses.

We report on lenses that operate over the visible wavelength band from 450 nm to beyond 700 nm, and other lenses that operate over a wide region in the near-infrared from 650 nm to beyond 1000 nm. Lenses were recorded in liquid crystal polymer layers only a few micrometers thick, using laser-based photoalignment and UV photopolymerization. Waveplate lenses allowed focusing and defocusing laser beams depending on the sign of the circularity of laser beam polarization. Diffraction efficiency of recorded waveplate lenses was up to 90% and contrast ratio was up to 500:1.

Thiol Adsorption on and Reduction of Copper Oxide Particles and Surfaces.

The adsorption of 1-dodecanethiol at room temperature and at 75 °C on submicron cuprous and cupric oxide particles suspended in ethanol has been investigated by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy. Thiol adsorption occurs in all cases via Cu-S bond formation, with partial dissolution of CuO at 75 °C and formation of a copper-thiolate complex replacement layer. Regardless of temperature, the surface of the CuO particles is essentially completely reduced to either Cu2O or metallic copper, as evidenced by loss of the characteristic Cu(2+) XPS features of dried powder samples. Companion ultrahigh-vacuum studies have been performed by dosing clean, oxygen-dosed, and ozone-treated single crystal Cu(111) with methanethiol (MT) gas at room temperature. In the latter case, the surface corresponds to CuO/Cu(111). XPS confirms MT adsorption in all cases, with an S 2p peak binding energy of 162.9 ± 0.1 eV, consistent with methanethiolate adsorption. Heating of MT-covered Cu(111) and oxygen-dosed Cu(111) leads to decomposition/desorption of the MT by 100 °C and formation of copper sulfide with an S 2p binding energy of 161.8 eV. Dosing CuO/Cu(111) with 50-200 L of MT leads to only partial reduction/removal of the CuO surface layers prior to methanethiolate adsorption. This is confirmed by ultraviolet photoelectron spectroscopy (UPS), which measures the occupied states near the Fermi level. For both the colloidal CuO and single crystal CuO/Cu(111) studies, the reduction of the Cu(2+) surface is believed to occur by formation and desorption of the corresponding dithiol prior to thiolate adsorption.

Thin waveplate lenses of switchable focal length--new generation in optics.

We present new lenses - waveplate lenses created in liquid crystal and liquid crystal polymer materials. Using an electrically-switchable liquid-crystal half-wave retarder we realized switching between focused and defocused beams by the waveplate lens. A combination of two such lenses allowed the collimation of a laser beam as well as the change of focal length of optical system.

Photocatalytic Activity and Fluorescence of Gold/Zinc Oxide Nanoparticles Formed by Dithiol Linking.

Monolayer-protected gold nanoparticles (AuNPs) with average diameters of 2-4 nm have been covalently attached to zinc oxide nanorods using dithiol ligands. Electron microscopy and Raman spectroscopy show that ozone treatment or annealing at 300 or 450 °C increases the average diameter of the AuNPs to 6, 8, and 14 (±1) nm, respectively, and decomposes the organic layers to various degrees. These treatments locate the AuNPs closer to the nanorods. Heating and subsequent ozone exposure changes the color of the as-prepared nanocomposite powder from blue to purple due to oxidation of the outer layer of the AuNPs, and heating to 300 °C changes it to pink due to oxygen desorption. ZnO nanorods have a bimodal photoluminescence spectrum that consists of an ultraviolet excitonic peak and a visible, surface defect-related peak. Ozone treatment and annealing of the nanocomposite decreases the intensities of both peaks due to quenching by the AuNPs, but the visible peak is affected less. The photocatalytic efficiency of the nanocomposites toward oxidative degradation of rhodamine B has been measured and follows the order 300 °C > 450 °C > ozone treated ≈ as-prepared ≈ bare ZnO. The greater efficiency of the annealed samples likely arises from decreased electron-hole pair recombination rates.

All-optical diffractive/transmissive switch based on coupled cycloidal diffractive waveplates.

Pairs of cycloidal diffractive waveplates can be used to doubly diffract or collinearly propagate laser radiation of the appropriate wavelength. The use of a dynamic phase retarder placed in between the pair can be utilized to switch between the two optical states. We present results from the implementation of an azo-based retarder whose optical properties can be modulated using light itself. We show fast and efficient switching between the two states for both CW and single nanosecond laser pulses of green radiation. Contrasts greater than 100:1 were achieved. The temporal response as a function of light intensity is presented and the optical switching is shown to be polarization independent.

Azobenzene liquid crystalline materials for efficient optical switching with pulsed and/or continuous wave laser beams.

This study compares optical switching capabilities of liquid crystal (LC) materials based on different classes of azobenzene dyes. LCs based on molecules containing benzene rings with nearly symmetrical pi-pi conjugation respond more efficiently to a cw beam than to a nanosecond laser pulse and maintain the changes induced by the beam for tens of hours. Using azo dye molecules containing two benzene rings with push-pull pi-pi conjugation we demonstrate high photosensitivity to both a cw beam as well as nanosecond laser pulse with only 1 s relaxation of light-induced changes in material properties. Even faster, 1 ms restoration time is obtained for azo dye molecules containing hetaryl (benzothiazole) ring with enhanced push-pull pi-pi conjugation. These materials respond most efficiently to pulsed excitation while discriminating cw radiation.

Study of azo dye surface command photoalignment material for photonics applications.

We provide detailed quantitative characterization of sulfonic bisazodye SD1 as a photoalignment material for photonics applications. The reversibility of photoalignment was tested for transformations between planar and 90 degrees twist orientation states in a liquid crystal (LC) cell using polarized UV light. No degradation was observed for 100 cycles of transformations. A given twist angle of the LC orientation was obtained in a single step, as well as in a sequence of gradually increasing angles. A hysteresis is revealed in the latter case for planar-twist-planar cycles. The material was used for obtaining patterned orientation of a LC polymer providing similarly good quality photoalignment for UV as well as visible light. High efficiency large area and high spatial frequency optical axis gratings (or, polarization gratings) were demonstrated on a polycarbonate substrate. We show the opportunity of obtaining photoalignment in a multilayer system with single exposure to a polarized light. Finally, we provide evidence of a positive feedback in the dynamics of photoalignment due to the orientational effect of an increasing number of aligned molecules.

Optical switching of liquid-crystal polarization gratings with nanosecond pulses.

Optical switching with single nanosecond laser pulses of 532 nm wavelength is reported using high-efficiency optical axis gratings made with a nematic liquid crystal doped with an azobenzene dye. The azobenzene dye we have synthesized exhibits enhanced photosensitivity at green wavelengths, allowing for low threshold switching (approximately 10 mJ/cm(2)). The dye is also characterized by fast relaxation of isomers, allowing for restoration of the diffractive properties of the grating within approximately 100 ms. Change of the diffraction efficiency of the zeroth-order beam from 10% to 70% is observed in a micrometer-thick material layer.

Encapsulation of zinc oxide nanorods and nanoparticles.

A simple method for encapsulating zinc oxide nanoparticles within an organic matrix is described that consists of dispersing them in an ethanolic solution, adding an organothiol, and stirring while heating. Electron microscopy, photoemission, Raman spectroscopy, and thermal gravimetric analyses demonstrate that partial dissolution of the oxide occurs, accompanied by encapsulation within a matrix consisting of a 1:2 zinc/thiol complex. Using this methodology, it is possible to surround ZnO within diverse matrices, including fluorescent ones. The process is demonstrated for 1-dodecanethiol (DDT) and fluorescent 2-naphthalenethiol (NPT). For DDT, ZnO nanorods become surrounded by a layer of the zinc-thiol complex that is greater than 100 A thick. In the case of NPT, significantly greater dissolution of the ZnO occurs, with the encapsulated rods taking on a spherical geometry, as evidenced by electron microscopy.

Characterization of optically imprinted polarization gratings.

We provide detailed description and characterization of specifics of the imprinting technique for fabrication of large-area and high-efficiency liquid crystal polymer polarization gratings. We show that the quality of polarization gratings imprinted with linear polarized light is as high as that of gratings obtained in the holographic process, while exhibiting twice larger diffraction angle. The cycloidal polarization pattern used for imprinting is obtained from a master polarization grating, and the importance of fine tuning of its peak diffraction wavelength to the wavelength of imprinting radiation is emphasized. Tuning of the peak diffraction wavelength of imprinted polarization gratings from UV to near IR was realized with the aid of multilayer structures. Since the imprinting process does not involve a holographic setup, it is insensitive to ambient conditions and vibrations and provides an opportunity for large scale production of polarization gratings.

Fabrication of liquid crystal polymer axial waveplates for UV-IR wavelengths.

We show the opportunity of fabricating axially symmetric waveplates fine tuned to a desired wavelength. High quality waveplates are obtained using liquid crystal polymer layers on photoaligning substrates extending their functional range from UV to IR wavelengths. We characterize the effect of the waveplate on laser beams showing formation of a doughnut beam with over 240 times attenuation of intensity on the axis. We pay attention that the power density is strongly reduced on the doughnut ring as well and use this opportunity for taking charge coupled devices (CCDs) out of a deep saturation regime. Strong deformation of the beam profile is observed when the vortex axis is shifted towards the periferies of the beam. We demonstrate feasibility of using this phenomenon for shaping the profile of light beams with a set of waveplates.

Polarization insensitive imaging through polarization gratings.

Liquid crystal polarization gratings exhibit high diffraction efficiency (approximately 100%) in thin material layers comparable to the radiation wavelength. We demonstrate that they can be combined for polarization-insensitive imaging and optical switching applications. A pair of closely spaced, parallel oriented, cycloidal polarization gratings is capable of canceling the diffractive property of an individual grating. As a result, the phase of the beam is not distorted, and holographic images can be formed through them. An anti-parallel arrangement results in a broader effective diffraction band and doubles the diffraction angle. Broadband diffraction spanning from 480 nm to beyond 900 nm wavelengths has been obtained for a pair of gratings with 500 nm and 633 nm peak diffraction wavelengths. Liquid crystal polymer cycloidal gratings were used in the study showing 98% diffraction efficiency over a large area, and allowed for the use of laser beams expanded to 25 mm. The characteristics of combined cycloidal gratings were tested with laser beams at both UV and red wavelengths.

Time-resolved studies of photoinduced birefringence in azobenzene dye-doped polymer films.

We measured transient photoinduced birefringence (delta n) in various azobenzene dye films by pumping with a nanosecond pulse at 532 nm and probing at 633 nm. The switch-on times for the photoinduced birefringence range from nanoseconds to milliseconds and are systematically related with the lowest optical transition energies for those films. Moreover, our results suggest that the transient photoinduced birefringence measurement is a convenient way to determine the relative energies of pi-pi(*) and n-pi(*) states in azo-based materials.

Observation of nonlinear transmission enhancement in cavities filled with nonlinear organic materials.

We show experimental and theoretical results for enhancement of nonlinear transmission (NT) in moderate finesse cavities filled with nonlinear organic materials (NLOM). Our design for enhancement of nonlinear transmission using micro NLOM cavities compared with reference samples of the same material show that single cavities can enhance the nonlinear response by a factor of 10 or greater under high-absorption conditions. Further enhancement can be achieved in multiple-cavity structures. Other advantages of the cavity structures for nonlinear transmission, such as a higher damage threshold and a broader NT band, are also discussed. Our initial experimental results show a threefold reduction in the nonlinear threshold fluence in a single cavity device compared directly to an identical sample without mirrors, in qualitative agreement with our calculations.

Novel photoluminescence properties of surface-modified nanocrystalline zinc oxide: toward a reactive scaffold.

Nanocrystalline zinc oxide has been functionalized with 11-triethoxysilylundecal to introduce chemical reactivity for subsequent molecular attachment while preserving its unique photoluminescence (PL) properties. Silane bonding is confirmed using FTIR and photoelectron spectroscopy, with a total Si concentration of 3 to 4 atomic %. PL measurements demonstrate a 2-fold enhancement of its UV peak and maintenance of its visible peak compared to control samples. Enhancement of the UV peak is likely due to a decrease in the surface-dependent nonradiative recombination process. These results lay the framework for sensor fabrication, with the aldehyde groups available to bind analytes that would alter the PL spectrum.