Stearic acid mediated growth of edge-on oriented bilayer poly(3-hexylthiophene) Langmuir films.

The growth and structural evolution of stearic acid (SA) blended poly(3-hexylthiophene) [P3HT] Langmuir and Langmuir-Blodgett (LB) films were studied using complimentary surface and interface sensitive techniques to understand the possibility of ordering and layering of promising charge carrier mobility polymers, at the air-water interface and on the transferred solid substrate. SA-induced and subsequent compression-induced transitions in P3HT structure, from aggregated-3D to soft-2D and from in-plane mixed to unmixed layer, are evident at low and high pressures, respectively. The blending of SA molecules enhances the amphiphilic character of P3HT, which reduces the extent of the out-of-plane aggregation to form edge-on oriented (EO) bottom side-chain folded-bilayer (f-BL) islands (of size ~60 nm) within SA monolayer (ML), of commensurate thickness (~2.6 nm). Further compression, gradually rejects the less hydrophilic f-BL islands from the mixed layer to form EO P3HT BL islands (of coverage in-tune with starting composition) on top of SA ML. The formation of nearly covered P3HT(BL)/SA(ML) structured film on solid substrate is evident for the first time, which (even of limited P3HT thickness) has immense importance in the device properties, as the current in the bottom-gated organic thin-film transistors is known to travel only within few ML region near gate-dielectric.

Evolution of Electronic Structures of Polar Phthalocyanine-Substrate Interfaces.

The electronic structures and core-level spectra of chlorogallium phthalocyanine (ClGaPc) molecules of different thicknesses (submonolayer to multilayer) adsorbed on a polycrystalline Au substrate and a highly oriented pyrolytic graphite (HOPG) substrate, before and after thermal annealing, were investigated using photoelectron spectroscopic techniques for better understanding the charge-transfer properties. The energy-level diagrams (ELDs) of the ClGaPc thin films are found to evolve with film thickness, substrate nature, and thermal annealing. The interfacial dipole moment in the active Au substrate and the molecular dipole moment in the inactive HOPG substrate mainly dictate the ELD. Annealed monolayer films on both the substrates seem to adopt a similar well-ordered Cl-up orientated molecular organization, which is quite interesting, as it certainly indicates a substrate-nature-independent energy minimum configuration. The strong interaction of the active Au substrate gives rise to additional charge transfer and state transfer (of Ga) as evident from the formation of a former lowest unoccupied molecular orbital (F-LUMO) level in the highest occupied molecular orbital (HOMO) region and a low binding energy peak in the Ga 2p3/2 core level. The presence of strong F-LUMO and molecular-dipole-related HOMOd levels in the predicted monolayer of well-ordered Cl-up oriented molecules on the Au and HOPG substrates, respectively, creates the optimum energy-level alignment (ELA) for both the systems, while the opposite shift of the vacuum levels in two different substrates makes the ionization potential (IP) for such a monolayer either minimum (on the Au substrate) or maximum (on the HOPG substrate), which is useful information for tuning the charge injection across the interface in organic semiconductor-based devices.

Chitosan-fatty acid interaction mediated growth of Langmuir monolayer and Langmuir-Blodgett films.

The interaction of chitosan with bio-membranes, which plays important role in deciding its use in biological applications, is realized by investigating the interaction of chitosan with stearic acid (fatty acid) in Langmuir monolayers (at air-water interface) and Langmuir-Blodgett (LB) films (after transferring it onto solid substrate). It is found from the pressure-area isotherms that the chitosan insertion causes an expansion of chitosan-fatty acid hybrid monolayers, which reduces the elasticity and make the film heterogeneous. It is likely that at low surface pressure chitosan is situated at the interface, interacting with stearic acid molecules via electrostatic and hydrophobic interactions whereas at high pressure chitosan mainly located at subsurface beneath stearic acid molecules. In the latter case the interaction is predominantly electrostatic yielding very small contribution to the surface pressure. The reduction of temperature of the subphase water allows more number of chitosan molecules to reach surface to increase the pressure/interaction. On the other hand, although pure chitosan is found difficult to relocate on the substrate from air-water interface due to its hydrophilic-like nature, it alongside stearic acid (amphiphilic molecules) can be transferred onto substrate using LB technique as evident from infrared spectra. Their out-of-plane and in-plane structures, as extracted from two complementary surface sensitive techniques- X-ray reflectivity and atomic force microscopy, are found strongly dependent on the chitosan mole fraction and the deposition pressure. These analysis of the film-structure will essentially allow one to model the system better and provide better insight into the interaction.

Kinetic and isotherm studies on adsorption of toxic pollutants using porous ZnO@SiO2 monolith.

Removal of toxic effluents (like dyes and pesticides) by cost-effective and user-friendly method is needed to provide sustaining the environment for civilization. Here, low-cost mesoporous silica monolith (SiO2) and silica supported metal-oxide (ZnO@SiO2) monolith were synthesized to reduce the solemn impact of toxic effluents. Batch experiments were performed to remove Alizarin (AZ), Paradol (PD), Acid blue-113 (AB) and Rhodamine-B (RD) from aqueous solution via synthesized monoliths. The influence of various parameters (like pH, contact time, temperature and adsorbate concentration) has been optimized. The maximum adsorption capacity of ZnO@SiO2 monolith is 625, 500, 714 and 555mg/g for AZ, RD, AB, and PD respectively. The adsorption for AZ, PD, AB, and RD is spontaneous and exothermic. The adsorption process can be well described by the pseudo-second-order kinetic model (high regression coefficients) and the Freundlich isotherm model (R2=0.97-0.99).