Tridentate benzylthiols on Au(111): control of self-assembly geometry.

A set of hexasubstituted benzene derivatives with three thiol groups in the 1, 3, 5 positions and varied aliphatic substituents in the 2, 4, 6 positions (Me3-BTMT, Et3-BTMT, ODe3-BTMT) has been synthesized and self-assembled on Au(111). The resulting self-assembled monolayers (SAMs) are characterized by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and electrochemistry. The molecular orientation and long-range order are affected by the "gear effect" of the hexasubstituted benzene ring and van der Waals interactions between the physisorbed alkyl chains drive. Me3-BTMT adopts a standing up orientation which results in the highest molecular surface density but also the lowest degree of chemisorption (1 to 2 Au­S bonds per molecule). In contrast, Et3-BTMT favors a lying down orientation with a greater number of surface-bonded thiol groups (2 to 3) per molecule, associated with the peculiar geometry of this molecule. Finally, ODe3-BTMT adsorbs mainly in a lying down orientation, forming the SAM with the highest degree of chemisorption (all thiol groups are gold-bonded) and the lowest molecular areal density.

Double-striped metallic patterns from PS-b-P4VP nanostrand templates.

A new nanometallic pattern, characterized by randomly disposed double or twin one-dimensional stripes and that adds to the nanotechnology toolbox, has been obtained from a unique template possessing the nanostrand morphology. This morphology had previously been shown to form in Langmuir-Blodgett films made from a polystyrene-poly(4-vinylpyridine) (PS-P4VP) diblock copolymer blended with 3-n-pentadecylphenol (PDP). The nanostrand backbone is composed of PS, and it is bordered along both sides by a P4VP monolayer, visualized for the first time by high resolution atomic force microscopy. The exposed P4VP alongside the nanostrands serves as sites for depositing compounds attracted selectively to P4VP. Here, both gold ions (HAuCl4·3H2O) and gold nanoparticles (AuNP, 12 nm in diameter, stabilized with sodium citrate) were complexed to the P4VP. Plasma treatment of the gold ions led to double stripes of monolayer metallic gold. To obtain dense deposition of AuNP in double rows, it was necessary to acidify the AuNP aqueous solution (pH 5.2 here). The achievement of the metallic double-stripe patterns also confirms the composition of the nanostrand morphology, which up to now had been deduced indirectly. The double-stripe pattern has possible applications for plasmonic lasers, energy transport, and biosensors.

High thermal stability of block copolymer-capped Au and Cu nanoparticles.

Producing solution-based metal nanoparticles that do not agglomerate at elevated temperatures remains challenging. We show that thermally stable Au and Cu nanoparticles can be prepared using polystyrene-poly(4-vinylpyridine) diblock copolymers as capping agents. These materials remain stable when their solutions are subjected to prolonged heating up to 160 °C for more than 48 h. These conditions are sufficient for applications in most wet chemical processes and reactions.

Directing the assembly of gold nanoparticles with two-dimensional molecular networks.

Lamellar patterns resulting from the adsorption of p-dialkoxybenzene derivatives on HOPG have been investigated as molecular templates for directing the assembly of thiol-capped gold nanoparticles (AuNP). STM characterization at the liquid-solid interface reveals the periodic arrangement of AuNP on top of the self-assembled molecular network (SAMN), spanning hundreds of nanometers. The resulting superlattices are notably different from the close-packed structures formed by spherical nanoparticles during evaporative drying. The templating effect is based on van der Waals interactions of the alkyl chains of the SAMN and AuNP, and the assembly efficiency is greatest when these chains are of similar length.

Understanding and controlling morphology formation in Langmuir-Blodgett block copolymer films using PS-P4VP and PS-P4VP/PDP.

This contribution offers a comprehensive understanding of the factors that govern the morphologies of Langmuir-Blodgett (LB) monolayers of amphiphilic diblock copolymers (BCs). This is achieved by a detailed investigation of a wide range of polystyrene-poly(4-vinyl pyridine) (PS-P4VP) block copolymers, in contrast to much more limited ranges in previous studies. Parameters that are varied include the block ratios (mainly for similar total molecular weights, occasionally other total molecular weights), the presence or not of 3-n-pentadecylphenol (PDP, usually equimolar with VP, with which it hydrogen bonds), the spreading solution concentration ("low" and "high"), and the LB technique (standard vs "solvent-assisted"). Our observations are compared with previously published results on other amphiphilic diblock copolymers, which had given rise to contradictory interpretations of morphology formation. Based on the accumulated results, we re-establish early literature conclusions that three main categories of LB block copolymer morphologies are obtained depending on the block ratio, termed planar, strand, and dot regimes. The block composition boundaries in terms of mol % block content are shown to be similar for all BCs having alkyl chain substituents on the hydrophilic block (such as PS-P4VP/PDP) and are shifted to higher values for BCs with no alkyl chain substituents (such as PS-P4VP). This is attributed to the higher surface area per repeat unit of the hydrophilic block monolayer on the water surface for the former, as supported by the onset and limiting areas of the Langmuir isotherms for the BCs in the dot regime. 2D phase diagrams are discussed in terms of relative effective surface areas of the two blocks. We identify and discuss how kinetic effects on morphology formation, which have been highlighted in more recent literature, are superposed on the compositional effects. The kinetic effects are shown to depend on the morphology regime, most strongly influencing the strand and, especially, planar regimes, where they give rise to a diversity of specific structures. Besides film dewetting mechanisms, which are different when occurring in structured versus unstructured films (the latter previously discussed in the literature), kinetic influences are discussed in terms of chain association dynamics leading to depletion effects that impact on growing aggregates. These depletion effects particularly manifest themselves in more dilute spreading solutions, with higher molecular weight polymers, and in composition regimes characterized by equilibrium degrees of aggregation that are effectively infinite. It is by understanding these various kinetic influences that the diversity of structures can be classified by the three main composition-dependent regimes.

Pressure-induced order transition in nanodot-forming diblock copolymers at the air/water interface.

Understanding and controlling the processes in block copolymer (BC) monolayers at the air/water interface during surface area compression is a key issue for producing ultrathin films of predetermined morphology with well-defined order and known dimensions. Langmuir isotherms of nanodot-forming BC monolayers generally display a plateau indicative of a 2D phase transition, which has been the subject of various interpretations in the literature. Here, based on investigations of Langmuir-Blodgett and Langmuir-Schaefer nanodot films of PS-P4VP mixed with 3-n-pentadecylphenol (PDP), we show by atomic force microscopy (AFM) that it involves a change in nanodot packing order (from quasi-hexagonal to quasi-square), argued to be a general phenomenon for nanodot BC monolayers. It is accompanied by system-specific conformational changes (as discussed in previous literature), which, in the present case, implicate PDP alkyl chain ordering, as deduced previously from in situ infrared data and indirectly supported here by AFM imaging.

π-conjugation and charge polarization in fluorene-dibenzothiophene-S,S-dioxide co-oligomers by Raman spectroscopy and quantum chemistry.

The Raman spectra of a series of fluorine (F)∕dibenzothiophene-S,S-dioxide co-oligomers (S) of different length and alternation sequences in their backbones (FSF, FFSFF, FSFSF, and FASAF; A is the -C≡C- bridge) have been recorded and simulated theoretically. It is shown that Raman spectroscopy is useful to probe π conjugation and ground state electron polarization in these molecules, phenomena directly related with the existence of intramolecular charge-transfer processes owing to the combination of electron donor (fluorene) and acceptor (dibenzothiophene-S,S-dioxide) groups. Their geometric, electronic, and vibrational properties have been studied by density functional theory B3LYP∕6-311G(2d,p) quantum chemical calculations and compared with those for fluorene homo-oligomers. Comparative studies in solution∕solid∕melted phase led to the conclusion that the Raman wavenumbers are also sensitive to intermolecular interactions.

Nanostrand formation of block copolymers at the air/water interface.

Langmuir-Blodgett monolayers consisting of a network of nanostrands have occasionally been reported in the literature, but are often coexistent with other morphologies, which is not useful for potential applications. With the use of PS-P4VP/PDP, a polystyrene-poly(4-vinyl pyridine) diblock copolymer of 12 mol % VP content mixed with 3-pentadecylphenol, it is shown that the disordered nanostrand network morphology can be obtained reproducibly and uniformly over large surface areas by spreading chloroform solutions of relatively high copolymer concentration. Use of a more slowly evaporating spreading solvent, 1,1,2,2-tetrachloroethane, and a low subphase temperature, 8-9 °C, results in much more densely aligned nanostrands. Poorly spreading solvents such as nitrobenzene produce the well-known fingerprint pattern often observed in spin- or dip-coated thin films of block copolymers. A mechanism for nanostrand network formation is proposed that involves the momentary formation of a fingerprint morphology in spreading drops followed by its breakup at the level of the mobile P4VP/PDP stripes as spreading continues, leaving P4VP-anchored PS nanostrands floating on the water surface.