Molecular orientation of evaporated pentacene films on gold: alignment effect of self-assembled monolayer

Pentacene films deposited on self-assembled monolayers (SAMs) bearing different terminal functional groups have been studied by reflection-absorption IR, grazing angle XRD, NEXAFS, AFM, and SEM analyses. A film with pentacene molecules nearly perpendicularly oriented was observed on Au surfaces covered with an SAM of alkanethiol derivative of X-(CH2)(n)-SH, with X = -CH(3), -COOH, -OH, -CN, -NH(2), C(60), or an aromatic thiol p-terphenylmethanethiol. On the other hand, a film with the pentacene molecular plane nearly parallel to the substrate surface was found on bare Au surface. A similar molecular orientation was found in thinner ( approximately 5 nm) and thicker (100 nm) deposited films. Films deposited on different surfaces exhibit distinct morphologies: with apparently smaller and rod-shaped grains on clean bare Au surface but larger and islandlike crystals on SAM-modified surfaces. X-ray photoemission electron microscopy (X-PEEM) was used to analyze the orientation of pentacene molecules deposited on a SAM-patterned Au surface. With the micro-NEXAFS spectra and PEEM image analysis, the microarea-selective orientation control on Au was characterized. The ability to control the packing orientation in organic molecular crystals is of great interest in fabricating organic field effect transistors because of the anisotropic nature of charge transport in organic semiconducting materials.     

Effect of the phase states of self-assembled monolayers on pentacene growth and thin-film transistor characteristics

To investigate the effects of the phase state (ordered or disordered) of self-assembled monolayers (SAMs) on the growth mode of pentacene films and the performance of organic thin-film transistors (OTFTs), we deposited pentacene molecules on SAMs of octadecyltrichlorosilane (ODTS) with different alkyl-chain orientations at various substrate temperatures (30, 60, and 90 degrees C). We found that the SAM phase state played an important role in both cases. Pentacene films grown on relatively highly ordered SAMs were found to have a higher crystallinity and a better interconnectivity between the pentacene domains, which directly serves to enhance the field-effect mobility, than those grown on disordered SAMs. Furthermore, the differences in crystallinity and field-effect mobility between pentacene films grown on ordered and disordered substrates increased with increasing substrate temperature. These results can be possibly explained by (1) a quasi-epitaxy growth of the pentacene film on the ordered ODTS monolayer and (2) the temperature-dependent alkyl chain mobility of the ODTS monolayers.     

Tetra-t-butyl magnesium phthalocyanine on gold: electronic structure and molecular orientation

In this work we have investigated the electronic structure and the molecular orientation of (t-Bu)(4)PcMg (tetra-t-butyl magnesium phthalocyanine) on polycrystalline and single crystalline gold substrates using photoemission spectroscopy and x-ray absorption spectroscopy, and we compare the results to the unsubstituted PcCu (copper phthalocyanine). The C 1s photoemission spectrum is described similar to unsubstituted relatives with an additional component for the aliphatic substituents. The variation of the excitation energy causes distinct differences in the shape of the C 1s spectrum, which is very useful for the analysis of the molecular orientation in the uppermost layer. It is shown that despite of the sterically demanding substituents, ordered sublimed films of (t-Bu)(4)PcMg are accessible, the orientation of the molecules, however, is different from the orientation of the unsubstituted relatives.     

Surface-enhanced raman spectra and molecular orientation of phthalazine adsorbed on a silver electrode

SERS from phthalazine adsorbed on an Ag electrode was investigated under several conditions of applied voltage and solution concentration. Spectral assignments of the Raman bands were successfully performed and two differently oriented adsorbates, i.e. flat and end-on species, were identified. The contribution of the image field to the SERS intensity was considerable.     

A new magic titanium-doped gold cluster and orientation dependent cluster-cluster interaction

The stability and structures of titanium-doped gold clusters Au(n)Ti (n=2-16) are studied by the relativistic all-electron density-functional calculations. The most stable structures for Au(n)Ti clusters with n=2-7 are found to be planar. A structural transition of Au(n)Ti clusters from two-dimensional to three-dimensional geometry occurs at n=8, while the Au(n)Ti (n=12-16) prefer a gold cage structure with Ti atom locating at the center. Binding energy and second-order energy differences indicate that the Au(14)Ti has a significantly higher stability than its neighbors. A high ionization potential, low electron affinity, and large energy gap being the typical characters of a magic cluster are found for the Au(14)Ti. For cluster-cluster interaction between magic transition-metal-doped gold clusters, calculations were performed for cluster dimers, in which the clusters have an icosahedral or nonicosahedral structure. It is concluded that both electronic shell effect and relative orientation of clusters are responsible for the cluster-cluster interaction.     

Effect of loop orientation on quadruplex-TMPyP4 interaction

G-quadruplexes are believed to be potential targets for therapeutic intervention and this has resulted in designing of various quadruplex interacting ligands. Moreover, reports about existence of quadruplex forming sequences across the genome have propelled greater interest in understanding their interaction with small molecules. An intramolecular quadruplex sequence can adopt different conformations, owing to different orientation of loops in the structure. The differences in the loop orientation can affect their molecular recognition. Herein, we have studied the interaction of 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H, 23H-porphine (TMPyP4), a well-known G quadruplex binding ligand with three DNA quadruplexes differing in loop orientations. Results obtained from UV, ITC, and SPR studies have coherently revealed that the TMPyP4 molecule shows preferential binding to parallel G-quadruplex ( c-myc and c-kit) over its antiparallel counterpart (human telomeric). The binding affinity for parallel quadruplex was (10(7)) 1 order of magnitude higher than that for antiparallel DNA quadruplex (10 ). The study shows two binding modes, stronger binding (10(7)) of TMPyP4 involving end stacking and a weaker external binding (10 ), while TMPyP4 shows only one binding mode with duplex with a binding affinity of the order of 10(6). Overall, the study emphasizes that differences in the loop orientation give rise to different conformations of quadruplex, which in turn govern its binding to small molecules, and thereby play a pivotal role in molecular recognition.     

Molecular orientation and film morphology of pentacene on native silicon oxide surface

The growth morphology and mechanism of pentacene films on native Si oxide surface have been studied by using high-resolution electron energy loss spectroscopy (HREELS), X-ray diffraction (XRD), and atomic force microscopy (AFM). Despite the good agreement between our own and the reported XRD results, the previous XRD interpretation that the pentacene molecules are tilt-standing on the substrate cannot explain our HREELS data. The HREELS results show that a substantial portion of the first two layers of pentacene molecules are tilted-standing or randomly oriented, whereas the upper-layer molecules are mostly lying flat to the substrate. AFM reveals that the first two layers of molecules form a flat and smooth surface, but the upper layers show a rough terrace structure with a mean-square roughness equal to the average thickness (without counting the first two layers). This relationship is explained by a theoretical model which assumes the pentacene molecules to remain on a particular molecule layer after arrival. The observed film growth morphology may have significant implication on the performance of electronic devices based on pentacene thin films. A plausible explanation was proposed for the discrepancy between the HREELS-indicated and the XRD-derived molecular orientations.     

A new type of soluble pentacene precursor for organic thin-film transistors

A new type of soluble pentacene precursor is synthesized, which extrudes a unit of CO upon heating at 150 degrees C, to produce pentacene in nearly quantitative yield.     

Bottom-up assembly of colloidal gold and silver nanostructures for designable plasmonic structures and metamaterials

We report on bottom-up assembly routes for fabricating plasmonic structures and metamaterials composed of colloidal gold and silver nanostructures, such as nanoparticles ("metatoms") and shape-controlled nanocrystals. Owing to their well-controlled sizes/shapes, facile surface functionalization, and excellent plasmonic properties in the visible and near-infrared regions, these nanoparticles and nanocrystals are excellent building blocks of plasmonic structures and metamaterials for optical applications. Recently, we have utilized two kinds of bottom-up techniques (i.e., multiple-probe-based nanomanipulation and layer-by-layer self-assembly) to fabricate strongly coupled plasmonic dimers, one-dimensional (1D) chains, and large-scale two-dimensional/three-dimensional (2D/3D) nanoparticle supercrystals. These coupled nanoparticle/nanocrystal assemblies exhibit unique and tunable plasmonic properties, depending on the material composition, size/shape, intergap distance, the number of composing nanoparticles/nanocrystals (1D chains), and the nanoparticle layer number in the case of 3D nanoparticle supercrystals. By studying these coupled nanoparticle/nanocrystal assemblies, the fundamental plasmonic metamaterial effects could be investigated in detail under well-prepared and previously unexplored experimental settings.     

The electronic structures and spectra of conducting pentacene derivatives

Theoretical studies of pentacene and a series of its derivatives were performed using the PM3 and DFT methods. Based on B3LYP/6-31G(d) optimized geometries, the electronic, IR, and ¹³C NMR spectra of the derivatives were calculated using the INDO/CIS, PM3, and B3LYP/6-31G(d) methods, respectively. The energy gaps of the derivatives decreased as the chain length increased and electron-withdrawing substituents were introduced. The polymer based on pentacene, especially in the presence of trimethylsilylacetylene, offers promise as an excellent conducting polymer. The main absorption bands in the electronic spectra of the derivatives compared with those of pentacene were shifted to the red, whereas the IR frequencies for some of the C=C and C-H bonds were shifted to the blue. The ¹³C chemical shifts of the carbon atoms connected with electron-withdrawing substituents were shifted upfield, while those of the bridged carbon atoms in the middle part of the pentacene unit shifted downfield.     

Experimental and theoretical studies on molecular structures and vibrational modes of novel compounds containing silver

The two novel silver containing complexes of N-(pyridin-2-yl)pyridin-2-amine (NDPA) molecule has been synthesized and characterized by elemental analysis, FT-Raman and FT-IR (at far and mid regions) spectroscopies. The optimized geometries of the compounds were obtained by using DFT/B3LYP method with LANL2DZ basis set for the (C₁₀H₉N₃) · AgNO₃ and B3LYP method with DGDZVP basis set for the (C₁₀H₉N₃) · AgClO₄. The vibrational frequencies and their IR and Raman intensities were determined by theoretical methods. In addition, the HOMO-LUMO energies, thermochemical properties and atomic charges for the complexes were obtained in same level of theory. The experimental and theoretical results show that the silver atoms are coordinated to ligands in bidentate fashion. In addition, in the structures of complexes there are intra-molecular interactions. The oxygen atoms of nitrate and perchlorate are bonded to ligand via hydrogen bonds.     

Effect of molecular orientation on the biodegradability of aliphatic polyester

The effect of morphological microstructure on the biodegradability of aliphatic polyester, poly(ϵ -caprolactone) (PCL) was studied in terms of crystallite size, crystallinity and amorphous and crystalline orientation factors. Microstructural changes during hydrolysis/biodegradation of the drawn PCL films were investigated by the conventional small and wide angle X-ray scattering methods. The lower was the draw ratio, the higher the hydrolytic degradability or biodegradability. With the increase of the hydrolysis time, the long period, at earlier stage, decreased; then slightly recovered and the crystallinity increased while the lamellar thickness remained unchanged. The amorphous orientation factors start to decrease at earlier stage and gradually go down to zero before the end of hydrolysis. In the case of crystalline orientation factor, although the values decrease with increasing hydrolysis time, they do not reach zero point. After the biodegradation for 60 days, crystallinity, crystal lateral size and lamellar thickness in all drawn PCL films decreased, and then it was confirmed that even crystalline regions were degraded for long term biodegradation test.     

Effect of molecular orientation on the swelling of nylon 6

The effect of molecular orientation on the linear swelling of nylon 6 caused by absorption of water was studied using two kinds of oriented films, melt drawn and cold drawn. The molecular orientation causes anisotropy in swelling at all humidities such that the swelling is larger in the orientation direction than in the directions perpendicular to it. The large contribution of crystalline orientation to this phenomenon was expected for the melt drawn film which has practically no amorphous orientation. An analysis with a two-phase morphological model reveals that the distance between the crystallites is a prominent factor controlling the degree of linear swelling, and that the anisotropy of swelling arises from the change in the distribution of crystallites due to orientation. By comparing the result for the melt drawn film with that for the cold drawn film, which has considerable amorphous orientation, it was proven that molecular orientation in the amorphous phase where swelling actually occurs does not depend so much on the degree of swelling as on the distribution of crystallites.     

Construction of conjugated molecular structures on gold nanoparticles via the Sonogashira coupling reactions

Functional, conjugated molecular structures have been fabricated on Au nanoparticles via the Sonogashira coupling reactions.     

Adsorption of mercury on gold and silver surfaces

In order to study the adsorption mechanism of Hg on Au and Ag substrates, thin film Au(111) and Ag(111) substrates were exposed to gaseous metallic mercury, while the mercury concentration, substrate temperature, and exposure length were varied. The resulting changes in the surface morphology of the substrates were studied with scanning tunneling microscopy (STM). The amount of adsorbed Hg required to cause saturation, i.e. a decrease in the adsorption rate was found to be dependent on the mercury concentration and substrate temperature. The observations lead to the conclusion that the adsorption includes place exchange processes and concerted adsorption of more than one Hg atom in one process. The results show that the collection efficiency of single-crystalline surfaces is a function of both mercury concentration and temperature. Therefore, results from measurements performed at different conditions using single-crystalline surfaces may not be comparable. Received: 3 February 1999 / Revised: 7 June 1999 / Accepted: 9 June 1999     

Effect of the metal nature on hemostatic activity of water-soluble gold and silver nanocomposites

The hemostatic activity of polymeric gold and silver nanocomposites depends on their kinetic stability caused by the interaction of the ligand with nanoparticles. The properties of the nanoparticles are determined by the metal nature.     

An interaction site model integral equation study of molecular fluids explicitly considering the molecular orientation

We implemented an interaction site model integral equation for rigid molecules based on a density-functional theory where the molecular orientation is explicitly considered. In this implementation of the integral equation, multiple integral of the degree of freedom of the molecular orientation is performed using efficient quadrature methods, so that the site-site pair correlation functions are evaluated exactly in the limit of low density. We apply this method to Cl(2), HCl, and H(2)O molecular fluids that have been investigated by several integral equation studies using various models. The site-site pair correlation functions obtained from the integral equation are in good agreement with the one from a simulation of these molecules. Rotational invariant coefficients, which characterize the microscopic structure of molecular fluids, are determined from the integral equation and the simulation in order to investigate the accuracy of the integral equation.     

Cysteine-assisted growth of silver on gold nanorods

Au–Ag core–shell (Au@Ag) nanobars could be synthesized from gold nanorod (NR) seeds with cysteine additives by a two-step process of reaction temperatures. The lateral sides of gold NRs surrounded by surfactant bilayers render cysteine additives binding on both ends of the NRs, and restricted silver deposition to their lateral sides at room temperature. Further, silver deposition can take place at first on the pre-formed silver layers on the lateral sides at higher temperatures and finally resulted in the formation of Au@Ag nanobars in which gold NRs are in the corner positions of the nanobars and their longitudinal axes parallel to the longer sides of the nanobars.