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The self-assembling properties of two rationally designed discotic π-conjugated hexaazatrinaphthylene (HATNA) molecules have been studied. In appropriate solvent systems, both ester-dodecyl-substituted and amide-dodecyl-substituted HATNAs self-assembled into nanowires and formed organogels. These nanowires could be easily transferred onto solid supports through spin casting for morphological study. In addition to the solution-based self-assembly method, solvent-vapor annealing (SVA) was explored as an alternative way to control the organization of supramolecular nanowires on surfaces. It was found that amorphous thin film of HATNA molecules transformed gradually into nanowire structures through a nucleation and growth mechanism during the SVA process. Several parameters including the preordering of molecules in the original thin film, choice of solvent vapors, annealing times, and surface properties were tuned to create different supramolecular organizations. Under particular conditions, aligned nanowires with preferential direction can be achieved.

One of the most challenging tasks encountered in developing highly efficient electro-optic (EO) devices is to find a material system that possesses all desirable properties such as large EO coefficients, good thermal and mechanical stability, and low optical loss. In order to meet this stringent requirement, we have developed a series of crosslinkable EO dendrimers using the standardized AJL8-type chromophore as the center core and the furyl- and anthryl-containing dendrons as the periphery. Upon adding a trismaleimide (TMI) dienophile, these dendrimers could be in-situ crosslinked via the Diels-Alder cycloaddition and efficiently poled under a high electric field. Through this dynamic process, the spatially voided and π-electron-rich surrounding of the chromophore core changes into a dense and more aliphatic network, with the dipolar chromophore embedded and aligned inside. The resultant materials exhibit large EO coefficients (63-99 pm V -1 at 1.31 μm), excellent temporal stability (the original r 33 values remain unchanged at 100 °C for more than 500 h), and blue-shifted near-IR absorption. With these combined desirable properties, a poled EOD2/TMI film could be processed through multiple lithographic and etching steps to fabricate a racetrack-shaped micro-ring resonator. By coupling this ring resonator with a side-polished optical fiber, a novel broadband electric-field sensor with high sensitivity of 100 mV m -1 at 550 MHz was successfully demonstrated.

A series of new hydrophobic two-photon absorbing (2PA) chromophores with varied electron-donating groups in quasi-linear and multibranched structures are synthesized to correlate their structure/photophysical property relationships. The feasibility of using these large two-photon absorption cross-sectional (δ, expressed in GM = 1 × 10–50 cm4 s photon–1 molecule–1) materials in aqueous solution is also explored. All four hydrophobic 2PA materials can be encapsulated into micelles generated by dispersing an amphiphilic block copolymer, poly(methacrylic acid)-block-polystyrene (PMAA-b-PS), into water. The micellar nanostructures are characterized using dynamic light scattering, atomic force microscopy, and transmission electron microscopy. After these dyes are incorporated into micelles, they exhibit strong fluorescence in water. It is found that the quantum yield and δ values of these chromophores are strongly dependent on the diameters of the micelles, concentrations of the PMAA-b-PS, and molecular structures of the 2PA chromophores. One of the compounds that has a strong triarylamino donor and a multibranched structure exhibits a large δ value of 2790 GM and high quantum yield (0.56) in micelle-containing water. Although this value is smaller than the original value of 5300 GM in toluene, it is still substantially larger than the values of most water-soluble 2PA materials, which have δ values of less than 100 GM.

Two series of highly efficient and thermally stable nonlinear optical chromophores based on the (4-diarylamino)phenyl electron donors have been synthesized and systematically investigated. A modular approach has been employed to synthesize these electron donors with tunable size, shape, and electron-donating abilities. Efficient conjugated bridges were extended from these donors and coupled with very strong CF3−TCF electron acceptors to afford chromophores with very high β values (up to 7077 × 10-30 esu at 1.907 μm). These chromophores possess much higher thermal stability (with their onset decomposition temperatures all above 220 °C) than those substituted with (4-dialkylamino)phenyl donors. Most importantly, the high molecular hyperpolarizability of these chromophores can be effectively translated into very large electro-optic (E-O) coefficients (r33) in poled polymers through suitable shape engineering. Exemplified by the chromophore B4, which has a fluorinated aromatic substituent anchored at its dono...

Three dendron−linear diblock copolymers with a polyene-type nonlinear optical (NLO) chromophore incorporated in the dendron segment and polystyrene as the linear block were synthesized to investigate the effect of nanostructures on electrooptic (EO) properties. These block copolymers form nanostructures with a periodicity between 36 and 44 nm, which can be characterized using atomic force microscopy (AFM). High EO coefficients (r33) up to 64 pm/V can be achieved in these materials that only have relatively low chromophore concentrations (the highest one is 18 wt %). The resulting poled copolymers also showed good temporal stability. More than 81% of the original r33 value can be retained after being isothermally heated at 85 °C for more than 500 h. On the contrary, the results from the guest−host systems (the chromophore was dispersed into polystyrene) only exhibited lower r33 values and very poor thermal stability (less than 30% of the original r33 values remained after 120 h at 85 °C). These results cle...

Poled electro-optic (EO) polymers have enabled many advances in the exploration of high-speed and broadband information technologies. Polymer based EO devices have been demonstrated to have large bandwidths (over 110 GHz), low driving voltages, and sustain their performance in a flexible form or under extreme environmental conditions. For optical circuits, EO polymers can be easily integrated with striplineor ring-structured waveguides made of sol–gels, low-loss fluorinated polymers, silicon slots, conducting oxides, and photonic crystals. Recently, EO polymers have also been utilized for the generation/detection of a gap-free pulsed THz system with a bandwidth up to ca. 12 THz. Large numbers of discrete photonic components need to be inserted into integrated systems of telecommunication and silicon microphotonics, especially where an extreme amount of data is required to travel in a very small space. Therein lies the great challenge for polymer-based EO technologies: to have thermally stable EO coefficients (r33) of around 500 pm V at wavelengths of 1.31 or 1.55 lm. Currently, the most commonly used materials for polymeric EO devices are based on poled polymers with r33 values around 50–80 pm V at wavelengths of 1.31 or 1.55 lm. In these materials, dipolar nonlinear optical (NLO) chromophores have been doped or incorporated at a level of ca. 20– 25 wt % to reach their maximum r33 values. [5–10] Beyond such a moderate loading of chromophores, strong intermolecular electrostatic interactions severely limit the poling-induced polar order and cause phase-separation problems between chromophores and polymers. To further improve EO activity, research efforts have focused on developing shape-engineered chromophores with high molecular optical nonlinearities (lb), where lb is a product of first hyperpolarizability and the dipole moment of the NLO chromophore, and increasing order within the matrices by controlling the nanoscale architecture of macromolecules. In our recent study we have demonstrated, using Diels–Alder (DA) “click chemistry” to post-functionalize NLO chromophores onto polymers, that high chromophore loading levels (up to 35 wt %) and large r33 values (up to 110 pm V) could be achieved in in situ generated side-chain dendronized NLO polymers with non-reacted chromophores as guest dopants. This opens a new avenue to explore optimal host–guest combinations and to develop an efficient way to control lattice hardening in these hybrid polymers. The ultimate goal is to simultaneously achieve very large EO activity, good thermal stability, high optical transparency, and excellent mechanical properties within the same material via molecular design and facile processing. In this paper, we report a novel method to disperse a highly efficient secondary chromophore into in situ crosslinked NLO polymer networks, leading to both enhanced EO activity (> 260 pm V at 1.31 lm) and alignment stability at 85 °C. In photorefractive (PR) polymers and liquid-crystal (LC) systems, binary chromophore mixtures have been shown to elevate the loading density of small dipolar dyes without causing phase separation. We have extended this further by incorporating highly polarizable NLO chromophores into these binary systems. In addition, DA click chemistry has also been employed to improve the physical properties of these materials. This combined effort demonstrates that binary mixtures of large-bl chromophores can be loaded into side-chain NLO matrices and efficiently poled to give EO activities higher than the summed value of two added chromophores. These systems can also be mildly cured to ensure a thermally stable EO response. The EO polymers studied in this work exist as a three-component host–guest system (Fig. 1). The host polymer is a copolymer, poly[(methyl methacrylate)-co-(9-anthracenyl methyl methacrylate)] (PMMA-AMA), with around 10 mol % of the anthracenyl moiety. To this host, AJC146 was added together with compound 1a, 1b, or 1c as binary guest chromoC O M M U N IC A TI O N S

We have synthesized a new class of highly efficient nonlinear optical (NLO) chromophores based on the novel tricyanopyrroline (TCP) electron acceptor. Molecular linear and nonlinear optical properties of the prototypical chromophores were measured and calculated to understand structure−property relationships. One such chromophore showed molecular first hyperpolarizability (β) of (8700 ± 702) × 10-30 esu at excitation wavelengths of 1.9 μm, and another showed macroscopic electro-optic (EO) coefficients (r33) of 51 pm/V at 1.55 μm with 20 wt % chromophore loading when poled with 65 V/μm in amorphous polycarbonate film. Synthetic strategies for extending the utility of the acceptor and chromophores are discussed.

We report the first structural data for bis(diarylamine) "bipolarons": we have isolated and crystallographically characterized salts of the dications obtained by two-electron oxidation of E-4,4'-bis[di(p-anisyl)amino]stilbene and E,E-2,5-bis{4-[di(p-anisyl)amino]styryl}-3,4-di(n-butoxy)thiophene, [1](2+) and [2](2+) respectively. ESR, NMR, and magnetometry suggest both species have singlet ground states. X-ray structures, together with (1)H NMR coupling constants for [2](2+), indicate geometries in which the bond lengths are shifted toward a quinoidal pattern relative to that in the neutral species, but not to a fully quinoidal extent. In particular, the bond-length alternations across the vinylene bridging groups approach zero. DFT calculations with closed-shell singlet configurations reproduce the observed structures well. Our results indicate that singlet species for which one might expect quinoidal geometries (with differences of ca. 0.1 A between formally single and double bonds) on the basis of a limiting valence-bond representation of the structure can, in fact, show structures with significantly different patterns of bond lengths.

A new organic semiconductor (BT-TTF) based on molecular moieties of benzothiadiazole and tetrathiafulvalene was designed and synthesized, and its structure, molecular packing and charge-transporting properties were determined. Thermal properties, electrochemical behaviors, and optical absorption of this molecule were studied by using differential scanning calorimetry/thermal gravimetric analysis, cyclic voltammetry, and ultraviolet-visible spectroscopy, respectively. Its bulk and nanowire single crystals were prepared and characterized by X-ray crystallography, scanning electron microscopy, transmission electron microscopy, and field-effect transistors. It is found that short intermolecular S···S (3.41 Å), S···C (3.49 Å), and S···N (3.05 Å) contacts define the solid-state structure of BT-TTF single crystals which π-stack along the [100] with interplanar distances of 3.49 Å. Solvent-cast single-crystal nanowire transistors showed mobilities as large as 0.36 cm2/(V s) with current on/off ratios of 1×10(6). This study further illustrates the impact of molecular design and a demonstration of high-performance single-crystal nanowire transistors from the resulting semiconductor.

Initial result of a TCO electrode based organic electro-optic modulator with new device structure which can achieve sub-1v, sub-1cm length is reported. High frequency structure design and simulation for 40GHz operation are discussed.

A novel organic Mach Zehnder EO modulator using TCO as electrodes has been demonstrated. The simulation results show such structure is suitable for high frequency operation by engineering TCO material conductivity and loss.

The one-dimensional (1-D) self-assembly property of an n-type hexaazatrinaphthylene (HATNA) discotic pi-conjugated molecule was studied. Structurally robust unimolecular columnar stacks of HATNA with tunable length have been fabricated through a combination of supramolecular self-assembly and post-polymerization approach. Moreover, microcontact printing can be utilized to transfer the self-assembled nanostructures to the surface to create desired functional patterns.

(E)-4,4'-Bis[bis(4-methoxyphenyl)amino]stilbene, 1, (E,E)-1,4-bis[4-[bis(4-methoxyphenyl)amino]styryl]benzene, 2, and two longer homologues, (E,E,E)-4,4'-bis[4-[bis(4-methoxyphenyl)amino]styryl]stilbene, 3, and (E,E,E,E)-1,4-bis(4-[4-[bis(4-methoxyphenyl)amino]styryl]styryl)benzene, 4, have been oxidized to their mono- and dications using tris(4-bromophenyl)aminium hexachloroantimonate. The intervalence charge-transfer (IVCT) band of 1(+) is narrow and asymmetric and exhibits only weak solvatochromism. Analysis of this band indicates that 1(+) is a class-III or class-II/III borderline mixed-valence species. In contrast, a broad, strongly solvatochromic IVCT band is observed for 2(+), indicating that this species is a class-II mixed-valence species. The assignment of 1(+ ) and 2(+) as symmetric class-III and unsymmetric class-II species, respectively, is also supported by AM1 calculations. Hush analysis of the IVCT bands of both 1(+) and 2(+) gives larger electronic couplings, V, than for their analogues in which the double bonds are replaced with triple bonds. The diabatic electron-transfer distance, R, in 1(+) can be estimated by comparison of the V estimated by Hush analysis and from the IVCT maximum; it is considerably less than the geometric N-N separation, a result supported by quantum-chemical estimates of R for 1(+)-4(+). In 3(+) and 4(+), the IVCT is largely obscured by an intense absorption similar to a band seen in the corresponding dications and to that observed in the monocation of a model compound, (E,E,E)-1-[bis(4-methoxyphenyl)amino]-4-[4-[4-(4-tert-butylstyryl)styryl]styryl]benzene, 5, containing only one nitrogen redox center; we attribute this band to a bridge-to-N(+) transition. The corresponding dications 1(2+)-4(2+) show a complementary trend in the coupling between redox centers: the shortest species is diamagnetic, while the dication with the longest bridge behaves as two essentially noninteracting radical centers.

Recent breakthroughs in developing exceptional organic electro-optic (EO) materials are reviewed. Whole series of guest-host polymers furnished with high μβ chromophores have shown large electro-optic coefficients around 100~160 pm/V @ 1.31μm. Moreover, new generation of NLO chromophores based on pyrroline and pyrrolizine acceptors have been designed and synthesized. To go beyond the typical oriented gas model limit for poled polymers, new approach of using nanoscale architecture control and supramoleaular self-assembly has been proved as a very effective method to create a new paradigm for materials with very exciting properties. The approaches of employing Diels-Alder reactions for postfunctionalization and lattice hardening also provide a facile and reliable way to generate high-performance EO polymers and dendrimers. This type of "click" chemistry paves the way to systematically study the relationships between chromophore shape and number density, controlled self-assembly, in addition to provide the material properties needed for multi-layer device fabrication. Finally, a new generation of binary monolithic glasses has been developed that exhibit unprecedented high EO activities through careful manipulation of intricate supramolecular interactive forces for self-assembly. The results obtained from these poled binary organic glass materials (r 33 as high as 310 pm/V at 1.31μm) are the highest values ever reported which are >10 times of the commercial lithium niobate crystals. The success of these material developments has recently inspired the exploration of new device concepts trying to take full advantage of the organic EO materials with ultrahigh r 33 values.

In this paper, we present a novel device structure for organic electro-optic modulators using transparent conducting oxides (TCOs) as electrodes to substantially reduce the switching voltage, and describe their fabrication. We report two different types of device geometry, a top conducting and a side conducting geometry, and discuss their strengths and weaknesses. We discuss how the voltage and speed performance of such modulators are dependant on the conductivity/optical loss ratio of the TCO electrodes. Our device simulation shows that by appropriately engineering the high TCO conductivity/optical loss ratio, 4-6x lower switching voltage can be achieved while still maintaining high modulation frequencies and low optical loss. We show that certain new TCO materials are capable of achieving the high conductivity/optical loss required for efficient modulation in the 1300-1550 nm wavelength range. We summarize the optical loss characteristics at 1300 nm of different types of thin-film TCO materials grown using different deposition techniques. TCO electrodes based on different types of materials, such as In 2 O 3 , ZnO, and ITO have been investigated for our device structures. Fabrication issues associated with the deposition of TCO electrodes directly on organic EO materials and our approach to addressing them are discussed. Initial results for organic EO modulators fabricated with TCOs as electrodes are presented, and the performance of these modulators are compared with theoretical modeling results. The new device structures presented here will enable next generation low-voltage organic EO modulators targeting RF photonics applications.

A series of side-chain electrooptic (E-O) polymers have been prepared by Diels-Alder reaction in a solid state and characterized for their nonlinear optical properties. A synthesized chromophore were easily attached to a pendent anthracenyl moiety functionalized on the poly(methylmethacrylate-co-anthrylmethylmethacrylate) thermally in the bulk films during the poling process without compromising E-O performances. We have also controlled a chromophore concentration to determine its critical loading density at which chromophore-chromophore electrostatic interaction occurs in the polymer matrix. The highest E-O coefficient was 110 pm/V for the 34 wt% of the doped chromophore in the polymer at the wavelength of 1.3 μm. A high loading density of chromophore was obtained without observing a severe phase separation in the polymer matrix by an AFM morphology study. This novel approach provides to demonstrate a strategy for developing highly efficient E-O materials with the full potential of a chromophore.

The E-4,4'-bis[di(p-anisyl)amino]stilbene cation is a class-III mixed-valence species with electronic coupling comparable to that in its biphenyl-bridged analogue, whereas its tolane-bridged analogue belongs to class II.

A series of molecular engineered organic glasses have been prepared to exploit the use of complementary Ar−ArF interactions to improve poling efficiency. These self-organized molecular glasses have also been used as host in the binary chromophore system to further improve the number density of chromophores and r33 values. Ultrahigh r33 values (up to 327 pm/V at the wavelength of 1310 nm) and good temporal stability could be achieved in these materials.

Pentacene-based organic thin-film transistors (OTFTs) have been fabricated using π-σ-phosphonic acid self-assembled monolayers (SAMs) on top of aluminum oxide as the gate dielectrics. With ultrathin dielectrics, high capacitances up to 760nF∕cm2 and low leakage current densities of 10−8A∕cm2 at 2V could be obtained, allowing operation of OTFTs within −3V. Vast improvements in the gate leakage current (∼2 orders), on/off current ratio (1 order), and subthreshold slope down to 85mV∕decade are achieved compared to control devices without SAMs. The OTFTs with pentacene vapor deposited at room temperature on SAM dielectrics-modified substrates exhibit mobilities of 0.14–0.30cm2∕Vs, on/off current ratios of 105, and threshold voltages of −(1.3–1.5)V.

Controlled assemblies of the n-type 5,6,11,12,17,18-hexaazatrinaphthylene (HATNA) molecule and its derivatives, 5,6,11,12,17,18-hexaazatrinaphthylene-2,8,14-tricarboxylic acid (HATNA–COOH) and 2,8,14-tri(3,4,5-tridodecyloxyphenylaminocarbonyl)-5,6,11,12,17,18-hexaazatrinaphthylene (HATNA-den), on Au(111) electrodes have been investigated using electrochemical scanning tunneling microscopy (ECSTM). Orientations of HATNA and HATNA–COOH molecules on Au(111) electrodes can be manipulated with potential modulation and imaged in situ by ECSTM. By increasing the applied electrode potentials, the HATNA and HATNA–COOH molecules were tuned at the solid/liquid interface to orient from parallel to perpendicular to the electrode surface because of dominating adsorbate–adsorbate interactions such as π–π stacking, hydrogen bonding, and weak dipole–dipole interactions and deprotonation of –COOH groups of the HATNA–COOH molecule at higher positive potentials. However, a stable adsorption orientation independent of applied electrode potentials was observed for the tridendron-containing molecule HATNA-den due to strong interactions between the alkyl chains and the Au(111) substrate, and between π-electrons of the aromatic rings and the Au(111) substrate. The ability to orient adsorbates and to change surface structures by controlling the substrate potential is a great boon to those attempting to create designer two-dimensional structures.