Surface-initiated synthesis of poly(3-methylthiophene) from indium tin oxide and its electrochemical properties

Poly(3-methylthiophene) (P3MT) was synthesized directly from indium tin oxide (ITO) electrodes modified with a phosphonic acid initiator, using Kumada catalyst transfer polymerization (KCTP). This work represents the first time that polymer thickness has been controlled in a surface initiated KCTP reaction, highlighting the utility of KCTP in achieving controlled polymerizations. Polymer film thicknesses were regulated by the variation of the solution monomer concentration and ranged from 30 to 265 nm. Electrochemical oxidative doping of these films was used to manipulate their near surface composition and effective work function. Doped states of the P3MT film are maintained even after the sample is removed from solution and potential control confirming the robustness of the films. Such materials with controllable thicknesses and electronic properties have the potential to be useful as interlayer materials for organic electronic applications.     

One-, two-, and three-photon absorption induced fluorescence of a novel chromophore in chloroform solution

One-, two-, and three-photon absorption induced fluorescence intensities of a novel nonlinear optical chromophore have been measured by using a tunable femtosecond pulsed laser as the excitation. Four resonance peaks are observed as the excitation wavelength is tuned from 600 to 2000 nm. These peaks correspond to the one-, two- and three-photon fluorescence resonance. Except for intensity difference, the lifetime and the fluorescence spectrum are found to be the same for the one-, two-, or three-photon resonance, hence suggesting that the same excited energy level is involved in emitting the fluorescence intensity. A three-level model is developed to account for the incident excitation laser intensity dependence of the one-photon and multiphoton fluorescence intensity. The model allows the multiphoton absorption cross sections to be extracted; it can also account for the deviation observed in the linear, square, and cubic intensity dependence of the one-, two-, and three-photon fluorescence intensity, respectively. To determine the absorption cross sections, the present method does not require the fluorescence quantum efficiency data, needed in the low intensity technique.     

Patterning of robust self-assembled n-type hexaazatrinaphthylene-based nanorods and nanowires by microcontact printing

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.     

Effect of intonation on cantonese lexical tones

In tonal languages, there are potential conflicts between the FO-based changes due to the coexistence of intonation and lexical tones. In the present study, the interaction of tone and intonation in Cantonese was examined using acoustic and perceptual analyses. The acoustic patterns of tones at the initial, medial, and final positions of questions and statements were measured. Results showed that intonation affects both the FO level and contour, while the duration of the six tones varied as a function of positions within intonation contexts. All six tones at the final position of questions showed rising FO contour, regardless of their canonical form. Listeners were overall more accurate in the identification of tones presented within the original carrier than of the same tones in isolation. However, a large proportion of tones 33, 21, 23, and 22 at the final position of questions were misperceived as tone 25 both within the original carrier and as isolated words. These results suggest that although the intonation context provided cues for correct tone identification, the intonation-induced changes in FO contour cannot always be perceptually compensated for, resulting in some erroneous perception of the identity of Cantonese tone.     

Systematic study of the structure-property relationship of a series of ferrocenyl nonlinear optical chromophores

A series of novel nonlinear optical (NLO) chromophores 1-4 incorporating the ferrocenyl (Fc) group as an electron donor and 2-dicyanomethylene-3-cyano-4-methyl-2,5-dihydrofuran (TCF) derivatives as electron acceptors are presented. The use of a constant Fc donor and varied acceptors and bridges makes it possible to systematically determine the contribution of the conjugated bridge and the acceptor strength to chromophore nonlinear optical activity. The X-ray crystal structures of all four chromophores allow for the systematic investigation of the structure-property relationship for this class of molecules. For example, the crystal structures reveal that both cyclopentadienyl groups in the ferrocenyl donor contribute to the electron donating ability. The first-order hyperpolarizabilities beta of these chromophores, measured by hyper-Rayleigh scattering (HRS) relative to p-nitroaniline are reported. These beta values are compared to those calculated by density functional theory (DFT). The excellent agreement between the theoretical and experimental beta values demonstrates that a linear relation exists between the hyperpolarizability and the bond length alternation. An electrooptic coefficient, r(33), of approximately 25 pm/V at 1300 nm, for compound 4, incorporated into a polymer matrix, is competitive with organic chromophores. Moreover, this r(33) is more than 30 times larger than the previously reported value for an organometallic chromophore in a poled polymer matrix. This work not only underscores the potential for Fc donor moieties, which have been underutilized, but also demonstrates that experimental characterization and theoretical simulations are now congruent, viable methods for assessing potential performance of NLO materials.     

Spin reorientation transition in single-domain

We demonstrate that the interplay of in-plane biaxial and uniaxial anisotropy fields in results in a spin reorientation transition and an anisotropic ac susceptibility which is fully consistent with a simple single-domain model. The uniaxial and biaxial anisotropy constants vary, respectively, as the square and fourth power of the spontaneous magnetization across the whole temperature range up to . The weakening of the anisotropy at the transition may be of technological importance for applications involving thermally assisted magnetization switching.     

Large tunneling anisotropic magnetoresistance in (Ga,Mn)As nanoconstrictions

We report a large tunneling anisotropic magnetoresistance (TAMR) in (Ga,Mn)As lateral nanoconstrictions. Unlike previously reported tunneling magnetoresistance effects in nanocontacts, the TAMR does not require noncollinear magnetization on either side of the constriction. The nature of the effect is established by a direct comparison of its phenomenology with that of normal anisotropic magnetoresistance (AMR) measured in the same lateral geometry. The direct link we establish between the TAMR and AMR indicates that TAMR may be observable in other materials showing room temperature AMR and demonstrates that the physics of nanoconstriction magnetoresistive devices can be much richer than previously thought.     

Effective in-device r33 of 735 pm/V on electro-optic polymer infiltrated silicon photonic crystal slot waveguides

We design and fabricate a 320?nm slot for an electro-optic (E-O) polymer infiltrated silicon photonic crystal waveguide. Because of the large slot width, the poling efficiency of the infiltrated E-O polymer (AJCKL1/amorphous polycarbonate) is significantly improved. When coupled with the slow light effect from the silicon photonic crystal waveguide, an effective in-device r(33) of 735?pm/V, which to our knowledge is a record high, is demonstrated, which is ten times higher than the E-O coefficient achieved in thin film material. Because of this ultrahigh E-O efficiency, the V(π)L of the device is only 0.44?V?mm, which is to our knowledge the best result of all E-O polymer modulators.     

STABILITY ANALYSIS OF PARAMETRICALLY EXCITED SYSTEMS USING SPECTRAL COLLOCATION

The spectral collocation method is used to determine the stability of parametrically excited systems and compared with the traditional transition matrix approach. Results from a series of test problems demonstrate that spectral collocation converges rapidly. In addition, the spectral collocation method preserves the sparsity of the underlying system matrices, a property not shared by the transition matrix approach. As a result, spectral collocation can be used for very large systems and can utilize sparse eigensolvers to reduce computational memory and time. For the large-scale system studied (up to 40 degrees of freedom), the spectral collocation method was on average an order of magnitude faster than the transition matrix approach using Matlab. This computational advantage is implementation specific; in a C implementation of the algorithm, the transition matrix method is faster than the spectral collocation. Overall, the method proves to be simple, efficient, reliable, and generally competitive with the transition matrix method.     

Directed assembly of single-walled carbon nanotubes via drop-casting onto a UV-patterned photosensitive monolayer

We report the use of a novel UV-sensitive self-assembled monolayer to selectively deposit single-walled carbon nanotubes from solution using heterogeneous surface wettability. This process combines ubiquitous photopatterning techniques with simple solution processing to yield highly selective and densely packed carbon nanotube patterns. The essential concept behind this process is the change in surface chemistry caused by the UV-induced monolayer reaction. Selective deposition of carbon nanotubes was achieved by drop-casting, and the resulting films show local ordering, indicating that further development of this process will lead to simple technique for large-scale integration.