The synthesis of mixed ligand orthometalated iridium(III) complexes as well as the characterization of their electro-optical properties is briefly illustrated. The cyclic voltammetry results exemplify an enhanced stability of the complex with a poly(ethylene glycol (PEG) side chain compared to the corresponding organometallic model material. Less degradation of the electrically active centers was found to occur on the electrode surface. Furthermore the morphology of thin films of the described polymeric material was investigated with respect to potential applications in thin film devices.

Uniform zinc sulfide spheres and multimers ranging in size from ∼ 90 nm to 1.0 micron were produced in large quantities by adding varying amount of supernatant in a secondary nucleation process. The particle morphology was investigated using scanning and transmission electron microscopy. Smaller particles exhibited increased surface roughness in the nitrate system. Characterization by x-ray and electron diffraction showed that the particles were built up from nanocrystallites. The relationship between the particle size, porosity, and refractive index was studied by modeling UV-Vis spectra using the Mie scattering method. Monodispersed zinc sulfide spheres and multimers in the size range from 100 nm to 600 nm can be used as high refractive index building blocks for photonic crystals with band gaps covering the entire visible spectrum as well as portions of the near-IR and UV regions.

We investigate the optical properties of a new class of wide-bandgap semiconductor based biomaterial system. We have synthesized a guanosine derivative with a strong dipole moment, which self-assemble in ∼ 50 –100 nm confined pits to form a ribbon like semiconductor structure (SAGC). SAGC were successfully self-assembled on GaN/AlN QD matrix and the luminescence from GaN QDs can be resonantly transferred to the SAGC molecules resulting in a significant enhancement in emission from the guanine molecules. We also propose the design of ultraviolet-visible photonic bandgap structures based on hybrid SAGC-GaN photonic crystal.

Thin films were prepared by depositing alternating layers of tungstate anion (WO42-) and poly(4-vinylpyridine-co-styrene) (PVP-S) onto an electrode from aqueous solutions. These films have very high contrast (CR > 8) relative to equivalent films prepared using poly(ethylene dioxythiophene) (PEDOT), but suffer from slow color change due to poor electrical conductivity. The switching time of the tungstate-based films was decreased by an order of magnitude, from 30 seconds down to three, by adding layers of indium tin oxide (ITO) particles stabilized with poly(diallyldimethylammonium chloride) (PDDA). In this case, a four-layer repeating structure was created (i.e., PVP-S and PDDA-ITO were each deposited every fourth layer). Unlike tungstate, ITO has a high intrinsic conductivity (∼ 104 S/cm) that accounts for the dramatic increase in the switching speed. It is only through the nanometer-scale control of film architecture, provided with the layer-by-layer (LbL) deposition process, that switching speed and contrast ratio can be optimized simultaneously.

This paper presents single particle fluorescence spectroscopy of perylene nanocrystals coupled with AFM observation of their topographic shapes. The fluorescence spectra of individual nanocrystals confirmed clearly and precisely a blue-shift in the excimer emission maximum on the reduction of their volume. The result can be explained in terms of “lattice softening”, which makes intermolecular interaction weaker and modified the energy level of the excimer state in nanocrystal.

This research is comprised of understanding the linear photophysical properties of various dyes to better understand the more complicated nonlinear optical properties. Determining structure property relationships of a series of structurally closely related chromophores is the key in understanding the drivers for the various photophysical properties. In this paper we survey the effect of physically changing the Pt poly-yne structure on the S0-S1 and T1-Tn absorption properties for each of the chromophores. A series of structurally modified platinum poly-ynes have been studied using experimental methods including UV/Vis absorption and nanosecond laser flash photolysis. We found that with extension of the ligand length both the ground and triplet excited state absorption shift to lower energies. Comparing the absorption properties of the ligands and butadiynes with the platinum containing versions reveal that the S1 and Tn exciton is localized on one portion of the ligand with extension and not conjugated through the whole molecule. Changing the phosphine R group results in little effect to the absorption properties except when the R group is conjugated in the case of phenyl. However, changing the R group results in varied materials properties.

We investigated and synthesized different orientation and substituted group of the thieno-pyridine framework organo-iridium complexes (PO-01, PO-02, PO-03). These materials exhibited yellow light. Fabrication of these emissive phosphorescent dopants with the device configuration of ITO/ NPB/ CBP: Ir-complex (4–6%) /BCP/Alq3/LiF/Al showed the EL emitting peak from 532nm to 564nm. The electroluminescent efficiencies of the devices were from 9.62 lm/W to 30.41 lm/W and maximum brightness was all above 7000 cd/m2. We demonstrated high-efficiency, high-brightness and saturated yellow Ir-complex phosphorescent materials for OLED.

Over the last decade, organic semiconductor thin film transistors have been the focus of many research groups because of their potential application in low-cost integrated circuits. Recently, an organic light-emitting field-effect transistor (OLEFET) was reported. In an OLEFET structure, optimal injection of both holes and electrons into the light-emitting layer are required for maximum quantum efficiency, whereas the gate serves as a controlling electrode. In this work, we achieved an OLFET structure with interdigitated hole-injecting Au and electron-injecting Ca contacts within a submicrometer channel length. Both contacts are bottom contacts to the upper-lying tetracene organic semiconductor. The study of IV-characteristics and light emission from these devices shined light on the underlying physics of the OLEFETs.

In order to achieve the near-ferroelectric order desired in organic electro-optic (EO) chromophore systems, a pseudo-discotic chromophore is under investigation. Calculations suggest head-to-tail inter-chromophore dipole-dipole interactions should drive chromophores with an appropriate aspect ratio into ferroelectric columns similar to those seen in discotic liquid crystals (DLCs). Therefore, the liquid crystalline properties of these chromophores are being examined by differential scanning calorimetery (DSC), polarized optical microscopy (POM), and X-ray diffraction (XRD). Furthermore, the effect of this discotic behavior on the order and EO properties of the system are being examined both dynamically by second harmonic generation (SHG) and statically by attenuated total reflection (ATR). Additionally, these chromophores are being incorporated into waveguide-based photonic devices.

A family of nonlinear optical chromophores has been synthesized containing novel donor systems based on functionalized guanidines. Chromophores utilizing these donor systems display superior transparency and stability properties. The unusual and highly desirable characteristics of these chromophores make them very promising candidates for electro-optic applications. Systematic study of the molecular hyperpolarizabilities and bulk electro-optic properties of polymers containing these chromophores is being used to guide optimization of these systems.

A family of new chiral metallocycles based on Pt(II) diimine metallocornors and bis(acetylene) bridging ligands have been synthesized, and characterized by a variety of techniques including 1H and 13C NMR, UV-visible, luminescence, infrared, and circular dichroism (CD) spectroscopies, and mass spectrometry. All metallocycles exhibit very strong phosphorescence with quantum yields of 8.3 to 15.7%. Chiral Pt(II)-based molecular squares were used as the light-emitting layer in multiplayer devices, and a maximum brightness of 5470 cd/m2 with a maximum luminous efficiency of 0.93 cd/A was achieved.

Analysis of the possible mechanisms of degradation of Ru(bpy)32+-based OLEDs has led to the idea of quencher formation in the metalloorganic area close to the cathode. It has been suggested that the quencher results from an electrochemical process where one of the bipyridine (bpy) groups is replaced with two water molecules [1] or from reduction of Ru(bpy)32+ to Ru(bpy)30 [2]. We have tested these and other degradation ideas for Ru(bpy)32+-based OLEDs, both prepared and tested with considerable exposure to the ambient environment and using materials and procedures that emphasize cost of preparation rather than overall efficiency. In order to understand the mechanisms involved in these particular devices, we have correlated changes in the devices' electrical and optical properties with MALDI-TOF mass spectra and UV-vis absorption and fluorescence spectra.

Organic memory cells have been constructed utilizing conducting polymer, poly(3-hexylthiophene), PHT. The PHT film with Au electrodes at the bottom was coated with ultra thin Al having the thickness of 1 nm on the top. The cell showed the large photoconductivity, which was measured between Au bottom electrodes. The photoconductivity lasted for several hours after turn off the illumination, indicating photo induced memory effect. The phenomenon is discussed in terms of the persistent photoconduction, which is resulted from the electron trapping at Al donor sites in the depletion layer formed near the top of film.

A new family of organic/inorganic hybrid silicate materials, bridged polysilsesquioxanes, was designed and synthesized through a molecular-level mixing technique. Since hybrid materials in the molecular-composite level, whose domain sizes are in the nanometer-scale, and whose constituents often lose individual identities and thus create new properties, we obtained a set of improved properties from those organically modified glasses. By modifying the Si-O-Si polymeric network, in this study, we produced controllable, porous hybrid glasses for facile and uniform doping of various ions, metals or semiconductor particles. By taking advantage of void volume created in those molecularly modified silicate systems, novel optical materials with designed properties can thus be achieved. Via a chemical strategy, we designed hexylene- or fluoroalkylene-bridged hybrid glasses doped with both Er+3 ions and CdSe nano-particles for the development of new laser amplifier materials. In photoluminescence experiments, a significant enhancement in fluorescence intensity at 1540 nm has been obtained from the fluoroalkylene-bridged glass. The presence of CdSe nano-particles, by virtue of their low phonon energy, also appears to significantly influence the nature of the surrounding environment of Er+3 ions in those modified silicate systems, resulting in the increased fluorescence intensity.

In the present work new luminescent materials with high quantum efficiencies based on layered double hydroxides (LDH) were obtained. Intercalation of complexes into the interlayer space of LDH doesn't affect their luminescent properties, forming non-volatile solid state material with good optical properties. The Coulomb interactions between LDH layers and complex can result in a change of complex structure in comparison with free complexes and in decreasing the number of the organic ligands per Ln atom. The energy transfer in the system was also studied.

An efficient flexible top-emitting organic light-emitting device (OLED) was fabricated on an aluminum-laminated polyethylene terephthalate substrate. A spin-coated light-emitting polymer layer was sandwiched between a silver anode and a multi-layered semitransparent cathode. The performance of polymer OLEDs was analyzed and compared with that of the devices having a conventional structure. An optical microcavity formed in the device enables to tune the emission color by varying the thickness of the active polymer layer. The OLEDs having a 110-nm-thick active polymer layer exhibited superior electroluminescence performance, with a turn-on voltage of 2.5V and a luminance efficiency of 4.56 cd/A at an operating voltage of 10V.

We report preliminary data on the infiltration of polystyrene opals with cyanine dye water solutions, which are known to form J-aggregates. Different approaches are used to infiltrate cyanines inside opals. The degree of infiltration is evaluated by scanning and transmission electron microscopy as well as micro reflectance spectroscopy. Data show that in spite of the low wettability of polystyrene with water solutions, some infiltration can be achieved. Even though this degree of infiltration is still not enough to observe strong modification on the photonic band structures, further strategies to improve it are in progress.

Polymer-metal composites offer the possibility of strongly enhanced nonlinear optical properties, which can be used for ultrasmall photonic devices. In this paper, we investigate numerically, by means of the finite-difference time-domain (FDTD) method, the propagation characteristics of surface plasmon polariton (SPP) modes excited in an optical nanowire consisting of a chain of either metallic cylinders or metallic spheres embedded in dielectric shells made of polymers (or other material) with optical Kerr nonlinearity. Our FDTD calculations incorporate both the nonlinear optical response of the dielectrics as well as the frequency dispersion of the metals, which is considered to obey a Drude-like model. It is demonstrated that, in the linear limit, the nanowire supports two SPP modes, a transverse and a longitudinal one, separated by Δλ = 20 nm. Furthermore, the dependence of the transmission of these SPP modes, on both the pulse peak power and Kerr coefficient of the dielectric shell, is investigated. Nonlinear optical phenomena, such as power-dependent mode frequency, switching, or optical limiting, are observed.

We study the role of a strong electron confinement on the surface-enhanced Raman scattering from molecules adsorbed on small noble-metal nanoparticles. We describe a novel enhancement mechanism which originates from the different effect that confining potential has on s-band and d-band electrons. We demonstrate that the interplay between finite-size and screening efects in the nanoparticle surface layer leads to an enhancement of the surface plasmon local field acting on a molecule located in a close proximity to the metal surface. Our calculations, based on time-dependent local density approximation, show that the additional enhancement of the Raman signal is especially strong for small nanometer-sized nanoparticles.

Recently we have demonstrated the potential of Atomic Layer Deposition (ALD) for the fabrication of advanced luminescent photonic crystal (PC) structures based on the inverse opal architecture.[1–3] PC's offer efficiency enhancement, decreased threshold, and other enhancements that improve phosphor performance. 3D PC structures are being extensively modeled, revealing that changes in the structures such as shifting the distribution of dielectric material can significantly improve photonic band gap (PBG) properties. For example, in the inverted “shell” structure, the width of the PBG can be increased from 4.25% to 8.6%.[4] Similarly, the PBG width can also be increased to 9.6% by formation of a non-close-packed structure.[5] Using the FDTD method, we have found that the PBG in a TiO2 non-closed packed structure can be as high as 5%. The performance of these structures depends critically on precisely and accurately placed high dielectric material. Using ALD, we have demonstrated infiltration of TiO2 films with extremely smooth surfaces (0.2–0.4 nm RMS roughness) while maintaining a high level of control over the infiltration coating thickness, enabling formation of composite infiltrated and inverse opals with nano-scale precision.

Here we report progress in fabrication of multi-layered and non-close packed PCs using ALD. Two and three-layer inverse opals were formed by the deposition of thin layers of ZnS:Mn and TiO2 in stacked configuration, each exhibiting luminescence when excited by UV light. Evidence for modification of the emission characteristics by high order PBGs (gaps other than between the 2nd and 3rd bands) has been observed. In addition, non-close packed inverse opals have been formed by infiltrating heavily sintered silica opals with TiO2, etching the spheres with hydrofluoric acid, and backfilling the resulting inverse opal. Resulting structures were characterized using specular reflectance and transmission, photoluminescence, and SEM. This work demonstrates the enormous potential that ALD offers for the realization of high performance photonic crystal structures.