We have investigated the development of erbium(III)-cored supramolecular complexes containing metalloporphyrins to circumvent the solubility problem and improve the optical amplification property. The new synthetic methodology was accomplished through the ligand-exchange model reaction using ErCl3 to optimize its synthetic condition We have designed and synthesized the model complexes to investigate coordination property between the ligand and the erbium ion. Highly coordinated erbium(III)-cored model complexes (at least 8 to 10 coordination) showed the strong near infrared(IR) emission at 1520 nm, corresponding to the 4I13/2 → 4I15/2 transition. Also, with these synthetic results, erbium(III)-cored supramolecular complexes based on metalloporphyrins were synthesized and characterized. They also showed the infrared emission of the 4I13/2 → 4I15/2 transition at 1520 nm.

Polyfluorenes are a class of polyaromatic macromolecules that are characterized by an alternating backbone structure that consists of a 9,9-dialkylfluorene unit in combination with another aromatic group. The nature of this aromatic unit plays a key role in the electronic properties of the polymers. For example, polyfluorenes which combine chromophoric and charge transporting aromatic units have received a great deal of attention over the last several years as the emissive layer in polymeric light emitting diodes [LUMATION* Light-Emitting Polymers (LEPs)]. More recently, polyfluorenes have also been designed to perform as the organic semiconducting layer in polymeric field effect transistors (PFETs). This effort has led to a class of polymeric semiconductors with an excellent combination of charge mobility, environmental stability, and processability. One such polymer is the polyfluorene based on an alternating backbone of 9,9-dioctylfluorene and 2,2'-bithiophene units. This material has been shown to have charge mobilities as high as 0.02 cm2/V-s with current on/off ratios of up to 106. The poly(fluorene-bithiophene) is more resistant to doping by atmospheric oxygen than other polymeric semiconductors such as poly(3-hexylthiophene). Inks based on solutions of poly(fluorene-bithiophene) in xylene, mesitylene, and other solvents have also been prepared. The paper will focus on the recent advances in the synthesis, fabrication, and electrical characterization of poly(fluorene-bithiophene). *Trademark of The Dow Chemical Company

Dipole emission pattern imaging experiments on single chains of common conjugated polymers (solubilized poly phenylene vinylenes) isolated by ink-jet printing techniques have revealed surprising uniformity in transition moment orientation perpendicular to the support substrate. In addition to uniform orientation, these species show a number of striking differences in photochemical stability, polarization anisotropy,[1] and spectral signatures[2] with respect to similar (well-studied) molecules dispersed in dilute thin-films. Combined with molecular mechanics simulation, these results point to a structural picture of a folded macromolecule as a highly ordered cylindrical nanostructure whose long-axis (approximately collinear with the conjugation axis) is oriented, by an electrostatic interaction, perpendicular to the coverglass substrate. These results suggest a number of important applications in nanoscale photonics and molecular-scale optoelectronics.

Fluorinated and photo-imageable precursors are synthesized through a Barbier-Grignard reaction for 1550-nm window. The precursors are used for the sol-gel process of integrated optic components for silica-on-silicon technology. Material compositions and process parameters are optimized to achieve internal absorptions >0.1 dB/cm and propagation losses of about 0.5 dB/cm at 1550 nm. Compact 1×16 Beam splitters are designed and fabricated which exhibit >0.3 dB power uniformity, >0.1 dB PDL and 1.5 dB coupling loss. By hybrid integration of the passive splitters and in-house fiber amplifiers, amplifying splitters are demonstrated at various signal intensities.

Cyclopentadithiophene based homopolymers and copolymers have been investigated as semiconductor layers in field effect transistors. They generally show low hole mobilities due to a disordered amorphous structure in the solid state. FET mobility can be enhanced in the homopolymer, although this results in poor on/off ratio of the device. The low mobilities may be attributed to the presence of solubilizing alkyl chains normal to the long axis of the polymer which prevent the self assembly of the polymer into an ordered π-stacked configuration.

Macrocyclic thiacalixarenes have interesting non-linear optical properties. Thiacalixarenes bearing phenylazo, imino, ethynylic groups or platinum derived acetylides on the upper rims were designed, prepared and fully characterised. They showed interesting properties for optical limiting. Moreover these macrocycles are highly soluble in organic solvents and can easily be embedded in inorganic matrix using the sol-gel routes.

Thiacalixarene based class I and II solid-state materials were prepared and their optical limiting behaviour was investigated.

Thin films (1-24 layers) of bis-zinc ethane-bridged porphyrin dimer (1) have been transferred on solid surfaces, by the Langmuir- Schäfer (LS) horizontal method. The related surface pressurearea isotherm curve shows that in dependence of the film pressure different condensed phases may occur in the monolayer. The inspection of the monolayer by Brewster Angle Microscopy (BAM) reveals the presence of peculiar networks whose structural features seemingly change upon film compression. On the other hand, the Scanning Force Microscopy (SFM) analysis performed on LS films shows fractal networks constituted by nanoscopic supramolecular aggregates, whose shape and size depend again on the LS deposition surface pressure. Finally, also UV-vis spectroscopy measurements indicates that the absorption is almost linearly related to the film thickness that is directly connected to the surface pressure.

Energy transfer from two polyphenylene-type polymers to a series of organic dyes was studied. One of the polymers was synthesized via Suzuki coupling of 1,4-phenyldiboronic acid with 1,4-dibromobenzene to obtain polyphenylene. The other polymer was a polybenzophenone generated by a nickel-mediated coupling of 2,5-dichloro-4'-methylbenzophenone. These polymers were used as the energy donors. A variety of Coumarins and other dyes were used as acceptors. Photophysical data and energy transfer parameters were determined.

As part of an effort to develop a spectroscopic structure-property relationship in platinum acetylide oligomers, we have prepared a series of bidentate Pt(PBu3)2L2 compounds. The ligand was the series o-syd-C6H4-CΞC-(C6H4-CΞC)n-H, n = 0,1,2. The terminal oligomer unit consisted of a sydnone group ortho to the acetylene carbon. The compounds were characterized by various methods, including 13C-NMR, ground state absorption, fluorescence, phosphorescence and laser flash photolysis. The acetylenic 13C-NMR resonances showed sydnone influences that decreased with increasing number of monomer units. The ground state absorption spectra were slightly red shifted from those of the baseline oligomers not having a sydnone group. The low temperature emission and excitation spectra showed complex dependence on excitation and emission wavelengths, suggesting the chromphores resided in a distribution of solvent environments and conformations. Finally, broad triplet state absorption spectra were observed, with absorption throughout the visible and near infrared regions.

Recently we found high and persistent spontaneous buildup of the surface potential upon vacuum vapor deposition of tris(8-hydroxyquinolinato) aluminum(III)(Alq3) on Au substrate under dark conditions (28 V for 560 nm thick Alq3 film). Such giant potential is removed by visible-light irradiation. These natures of the film suggest the possible applications to various organic devices such as memory devices. In this study, we investigated the retention time of the giant potential and the mechanism of the light-induced depolarization in order to discuss the feasibility of the device applications. The observed decay rate of the surface potential in vacuum condition was roughly 10 % loss in 10 years, which is enough for memory devices. As to the decay rate by light-irradiation, the observed rate was successfully reproduced by a theoretical simulation based on the photo-induced randomization of oriented Alq3 molecules.

An alkoxyphenyl substitutued new polyfluorene derivative, poly(9,9-bis(4'-n-octyloxyphenyl) fluorene) (PBOPF) was synthesized through Ni(0) mediated polymerization. Blue light-emitting PBOPF shows peak PL at 426 nm. No significant excimer emission was observed even after annealing the polymer film at 100 oC for 2h. Aseries of random copolymers of 2,7-dibromo-9,9-bis(4'-n-octyloxyphenyl)) fluorene (BOPF) and 2,7-dibromo-N-(2'-ethylhexyl)carbazole (EHC) were also synthesized through Ni(0) mediated polymerization. Carbazole comonomer was introduced to improve hole-transporting properties of PBOPF. The synthesized poly(BOPF-co-EHC)s showed similar UV-visible absorption and PL emission to PBOPF. EL devices were fabricated in an ITO/PEDOT/polymer/Ca/Al configuration. The EL devices using copolymers showed improved device performance than the device using PBOPF homopolymer due to a more balanced charge transport.

Organic polymer based thin-film transistors (OP-TFTs) look very promising for flexible organic electronics. In this paper, we describe devices based on a gate-planarized structure and using spin-coated organic polymer. We have analyzed the role of the device source and drain contacts and we present data indicating Schottky behavior of the contacts in OP-TFTs. In addition, we describe a quantitative evaluation of the source drain series resistances and extract the OP-TFT intrinsic electrical parameters.

We report here methods of surface modification and device construction which consistently result in lab-scale pentacene-based TFTs with mobilities at or above 5 cm2/Vs. Surface modifications include polymeric ultrathin films presenting a passivated interface on which the semiconductor can grow. High performance TFTs have been fabricated on a variety of dielectric materials, both organic and inorganic, and are currently being implemented in manufacturable constructions. Our surface modifications have also proven useful for substituted pentacene materials and for a variety of other organic semiconductors. In addition, we report an all organic active layer, rf-powered integrated circuit. Further experiments and statistical analyses are underway to explain the elevated mobility in our samples, and efforts have been made to confirm these results through collaboration.

We report a new method of Thin Crystal Film deposition. In the present paper we describe the method of crystallization, structure, and optical properties of Bisbenzimidazo[2,1-a:1',2',b']anthra[2,1,9-def:6,5,10-d'e'f']-diisoquinoline-6,9-dion (mixture with cis-isomer) (abbreviated DBI PTCA) sulfonation product. The Thin Crystal Film has a thickness of 200-1000 nm, with anisotropic optical properties such as refraction and absorption indices. X-ray diffraction data evidences a lyotropic liquid crystalline state in liquid phase and crystalline state in solid film. Anisotropic optical properties of the film make it useful in optical devices, e.g. liquid crystal displays.

Aluminum tris-(quinoline-8-olate) (Alq3) is the most widely used electron transport material for organic light emitting diodes. The Alq3 molecule exists as two different isomers: meridianal and facial, which differ by the symmetry of the arrangement of ligands around the aluminum ion. Various crystalline polymorphs of Alq3 have been identified to contain one of these isomers. In this paper we present experimental results that show that the facial and meridianal isomers of Alq3 can be distinguished in the solid state by 27Al nuclear magnetic resonance (NMR) spectroscopy under magic angle spinning (MAS). Our results prove that the recently discovered δ-phase of Alq3 exclusively contains the facial isomer. The same technique is also used to characterize the amorphous deposit of Alq3 showing that it is the meridianal isomer that predominantly exists in the amorphous state.

Pentacene is one of the most promising organic materials for organic transistor fabrication, since it offers higher mobility, better on-off ratio, improved environmental stability, and better reliability than most other organic semiconductors. However, its severe insolubility renders it useless for the solution-based fabrication of electronic devices. Solution-based processing is the key to enabling ultra-low-cost circuit fabrication, since it eliminates the need for lithography, subtractive processing, and vacuum-based film deposition. Using a recently developed soluble pentacene precursor, we demonstrate the first inkjet-printed pentacene transistor fabricated to date. This is achieved using a substrate-gated transistor structure in conjunction with an inkjetprinted pentacene precursor active layer. After deposition, the precursor is converted to pentacene via heating, through the decomposition of the Diels-Alder product. As the anneal temperature increases above 120°C, performance increases dramatically. The process is therefore compatible with numerous low-temperature plastics. As the anneal time is increased to several minutes, performance likewise increases through increased precursor decomposition. However, exposure to excess temperatures or times tends to degrade performance. This is caused by morphological and chemical changes in the pentacene film. Optimization of the anneal process alone has resulted in the demonstration of transistors with an on-off ratio of >105 and field-effect mobility of >0.01cm2/V-s, attesting to the great promise of this material.

We present organic field-effect transistors with dihexylquaterthiophene (DH4T) as active material, a derivative of the oligothiophene á-4T with two hexyl chains as end groups. This substitution makes this molecule suitable not only for vacuum sublimation but also for solution processing which enables cheaper production. Additionally, the layer ordering is improved. We compare vacuum deposited and solution processed OFETs based on DH4T. The former ones show nearly ideal I-V characteristics. The latter ones show deviations from ideal behavior and lower currents. Furthermore, temperature dependent measurements of drain-source current in vacuum deposited DH4T-OFETs shows an unusual variation of the OFET apparent mobility. These apparent changes in mobility are caused by a threshold voltage shift, which becomes pronounced at around 290 K

Monodisperse oligo(phenylenevinylene)s end-capped with arylamines have been prepared via Horner Olefinations from bisphosphonates and arylaminobenzaldehydes. The influences of the conjugation length, different arylamine end groups, and of side chains with various electronic character on the electrical and optical properties of the chromophores are investigated. The elongation of the π-conjugated segment from 3 to 5 rings gives rise to bathochromic shifts of the electronic spectra and a slight increase of the oxidation potential. The same but more pronounced is true when the central electron donating ethers are replaced by the strong acceptor alkylsulfone. The electronic spectra of chromophores with triphenylamine and with N-alkylphenothiazines as end groups are quite similar, but the heterocyclic unit reduces the oxidation potential. The incorporation of a chromophor into a segmented copolymer has only negligible effect on the optical and electrical properties.

We introduce a simple “solvent quenching” approach to align the rigid-rod à-helical poly(α-benzyl-L-glutamate) (PBLG) chains in the surface-grafted monolayer. By sequentially treating with a good solvent and a poor solvent, a unidirectionally aligned PBLG monolayer with an average tilt angle as small as 3° is obtained.

Interfacial band offset and band bending of organic semiconductors are critical to understand and improve organic photovoltaic cells. In this study, the energy level alignment of fullerene(C60) / metal-free phthalocyanine (H2Pc) interface which is one of the model interfaces of organic photovoltaic cells has been investigated using UV and X-ray photoemissions. For both ‘H2Pc on C60’ and “C60 on H2Pc' interfaces, 0.3 eV downward energy level shift was observed in XPS at the interface formation. This energy shift is quite steep in contrast to the band bending observed for C60/metal interfaces in our previous study, where thickness of 500nm was required to achieve 0.21eV band bending to get Fermi level alignment between metal electrode and C60. To clarify the origin of the band bending, the effect of the insertion of C60-H2Pc co-deposited layer between C60 and H2Pc layers was also investigated. The result suggested that possible doping of H2Pc to C60 is not main origin of the observed energy shift. We also found that the vacuum level shift at H2Pc/C60 interface is strongly dependent on the deposition sequence of the interface formation.