The aggregation properties of a standard conjugated polymer, poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), in two distinct solvents (chloroform and toluene) and a range of polymer concentrations (c = 0.1-3 mg/mL) have been unequivocally resolved using combined dynamic and static light scatterings (DLS/SLS). The prime challenges for analyzing this peculiar, practically important, solution system arise from the wide size distribution and unknown aggregate morphology, as well as pronounced interferences between translational and internal motions of aggregate clusters of considerably varying size. To cope with these central difficulties, we propose a self-consistent formulation for analyzing the dynamic structure factor in DLS experiment by extending an existing theory on free-draining bead-spring chains that explicitly accounts for internal fluctuations, along with two candidate form factors on Gaussian coil and rigid sphere, respectively, serving as two limiting cases to be discriminated in combined DLS and SLS measurements. Given that no accessibility to ultrasmall angular resolutions is a prerequisite, the suggested protocol can readily be carried out in conventional light-scattering apparatus. The present analyses unanimously support the rigid-sphere form factor in describing the entire set of light-scattering data on MEH-PPV solutions, differing from early small-angle neutron/X-ray scattering interpretations suggesting certain 2D fractal structures for the aggregation network. Scrutiny into the interior dynamics of aggregate clusters further disclosed that the segmental motions are noticeably more suppressed than for usual, nonaggregated polymer solutions, and no existing theories based on the bead-spring picture can yet capture the observed scaling behavior as manifested by the present data. Accordingly, we report several first-revealed properties of MEH-PPV solutions on the aggregate morphology, the size distribution (and mean size), mean aggregation number, and interior segmental dynamics, which serve as valuable information for linking solution properties with those for dried thin films in contemporary applications with conducting conjugated polymers.

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The growth of semiconductor crystals and thin films plays an essential role in industry and academic research. Considering the environmental damage caused by energy consumption during their fabrication, a simpler and cheaper method is desired. In fact, preparing semiconductor materials at lower temperatures using solution chemistry has potential in this research field. We found that solution chemistry, the physical and chemical properties of the substrate surface, and the phase diagram of the multicomponent compound semiconductor have a decisive influence on the crystal structure of the material. In this study, we used self-assembled monolayers (SAMs) to modify the silicon/glass substrate surface and effectively control the density of the functional groups and surface energy of the substrates. We first employed various solutions to grow octadecyltrichlorosilane (OTS), 3-mercaptopropyl-trimethoxysilane (MPS), and mixed OTS-MPS SAMs. The surface energy can be adjusted between 24.9 and 50.8 erg/cm(2). Using metal sulfide precursors in appropriate concentrations, AgIn5S8 crystals can be grown on the modified substrates without any post-thermal treatment. We can easily adjust the nucleation in order to vary the density of AgIn5S8 crystals. Our current process can achieve AgIn5S8 crystals of a maximum of 1 μm in diameter and a minimum crystal density of approximately 0.038/μm(2). One proof-of-concept experiment demonstrated that the material prepared from this low temperature process showed positive photocatalytic activity. This method for growing crystals can be applied to the green fabrication of optoelectronic materials.

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