Polyelectrolyte Poly Styrene Sulfonate Research Articles

Enhancing Efficiency of Nonfullerene Organic Solar Cells via Using Polyelectrolyte-Coated Plasmonic Gold Nanorods as Rear Interfacial Modifiers.

Sufficient sunlight absorption and exciton generation are critical for developing efficient nonfullerene organic solar cells (OSCs). In this work, polyelectrolyte polystyrenesulfonate (PSS)-coated plasmonic gold nanorods (GNRs@PSS) were incorporated, for the first time, into the inverted nonfullerene OSCs as rear interfacial modifiers to improve sunlight absorption and charge generation via the near-field plasmonic and backscattering effects. The plasmonic GNRs effectively improved the sunlight absorption and enhanced the charge generation. Meanwhile, the negatively charged PSS shell ensured the uniform dispersion of the GNRs on the surface of the photoactive layer, optimized the interfacial contact, and further promoted the hole transport to the electrode. These concerted synergistic effects augmented the efficiency (10.11%) by nearly 20% relative to the control device (8.47%). Remarkably, the ultrathin (∼2.2 nm) organic layer on the surface of GNRs was closely examined by acquiring the carbon contrast image through energy-filtered transmission electron microscopy (EF-TEM), which clearly confirmed the coating uniformity from the side to end-cap of GNRs. The surface plasmon resonance (SPR) effect of the GNRs@PSS on the surface of the photoactive layer was unprecedentedly mapped by photoinduced force microscopy (PiFM) under the illumination of a tunable wavelength supercontinuum laser mimicking sunlight. Furthermore, investigations into the effect of size, surface coverage, and incorporation location of GNRs@PSS on the performance of OSCs revealed that the appropriate design and incorporation of the plasmonic nanostructures are crucial, otherwise the performance can be decreased, as evidenced in the case of front interface integration.

Molecular aggregates of pyronin dyes with polyelectrolyte polystyrene sulfonate (PSS) in aqueous solution

Aggregation of the cationic dyes pyronin B (PyB) and pyronin Y (PyY) in aqueous solution containing anionic polyelectrolyte polystyrene sulfonate (PSS) has been studied by using steady-state and time-resolved fluorescence and UV–vis absorption spectroscopy techniques. Although H-aggregates of these pyronin dyes have been previously observed in colloidal suspension, this is the first report of their J-aggregates obtained as a function of dye concentration by using constant concentration of PSS in solution. The best dye concentrations for the J-aggregates were determined as 2.4 × 10−5 M and 1.2 × 10-4 M for PyB and PyY, respectively. Moreover, aggregation equilibrium constants (KD) and thermodynamic functions were determined as a function of temperature for H-type aggregation. By employing the exciton theory, angle (α) between the molecular transition dipole moments and the long aggregate axis, and the intermolecular distance (R) were also calculated for each dye aggregates. In addition, the fluorescence lifetime values were determined from fluorescence decay measurements for the monomer and aggregated species of pyronin compounds in polyelectrolyte aqueous solution.

The Fast Relaxation Process between Hydrophobically Modified Associating Polyacrylamide and Different Surfactants at the Water‐Octane Interface

In our previous work (Macromolecules 2004, 37:2930), we found that the hydrophobic blocks of polyacrylamide modified with 2‐phenoxylethyl acrylate (POEA) and anionic surfactant sodium dodecyl sulfate (SDS) may form mixed associations at octane/water interface. However, the process involving the exchange of surfactant molecules between monomers and mixed associations in interface is so fast that we cannot obtain its characteristic time. In this article, the interfacial dilational viscoelastic properties of another hydrophobically associating block copolymer composed of acrylamide (AM) and a low amount of 2‐ethylhexyl acrylate (EHA) (<1.0 mol%) at the octane‐water interfaces were investigated by means of oscillating barriers method and interfacial tension relaxation method respectively. The influences of anionic surfactant SDS and nonionic surfactant Triton X‐100 on the dilational viscoelastic properties of 7000 ppm polymer solutions were studied. The results showed that the interaction between P(AM/2‐EHA) and SDS was similar to that of P(AM/POEA) and SDS. Moreover, we got the relaxation characteristic time of the fast process involving the exchange of s Triton X‐100 molecules between monomers and mixed associations. We also found that the interfacial tension response of hydrophobically associating water‐soluble copolymers to the sinusoidal oscillation of interfacial area at low bulk concentration is as same as that of the typical surfactants: the interfacial tension decreases with the decrease of interfacial area because of the increase of interfacial active components. However, the interfacial tension increases with the decrease of interfacial area at 7000 ppm P(AM/2‐EHA), which is believed to be correlative with the structure of absorbed film. The results of another hydrophobically associating polymer P(AM/POEA) and polyelectrolyte polystyrene sulfonate (PSS) enhanced our supposition. The phase difference between area oscillation and tension oscillation has also been discussed considering the apparent negative value.

Electrostatic interactions of cationic dyes with negatively charged polyelectrolytes in aqueous solution

The electrostatic binding of the cationic dyes rhodamine 6G (R6G), acridine orange (AO), bisindolenylpentamethine (Cy5) and 1,1′-diethyl-2,2′-cyanine (PIC) to the anionic polyelectrolyte polystyrene sulfonate (PSS) was investigated by absorption and fluorescence spectroscopy. R6G exhibits little changes in the absorption and fluorescence spectra upon binding to PSS. Adsorption of Cy5 to PSS shifts the absorption 10 nm to the red, if the dye/polymer ratio ( D/ P) is below 0.1. This is caused by polarization of the extended π-electron system through the PSS charges. Larger D/ P ratio results in the formation of H-aggregates. Transition dipole interactions between the dye molecules shifts the absorption band to higher energy and quenches the fluorescence. This effect is even more pronounced in case of AO bound to PSS. Adsorption of the non-fluorescent dye PIC on PSS lead to a narrow fluorescence emission caused by formation of PIC J-aggregates. The J-aggregates requires a sterical fit of the aggregate structure to PSS binding sites, which is optimal fulfilled at a D/ P ratio of 0.55. Adsorption of more dye destroys the J-aggregates again, which is explained by a model of the J-aggregate–PSS complex. The study of competitive binding between AO, Cy5 and poly(allylamine) hydrochloride (PAH) onto PSS showed comparable binding constants for the dyes but a remarkably higher one for PAH.

Ellipsometry and x-ray reflectometry characterization of self-assembly process of polystyrenesulfonate and polyallylamine

Self-assembly of polyelectrolytes-polystyrenesulfonate (PSS) and polyallylamine (PAH) with added salts of MnCl and NaBr was studied by x-ray reflectometry and ellipsometry technique. The thickness of PSS-PAH bilayer was measured to be 5.1±0.2 nm according to reflectometry and 6.1±0.7 nm according to ellipsometry. The discrepancy in data is attributed to the difference in the interaction of the interfaces with x-rays and visible light. The films are found to be rather homogeneous and the deposition process regular. The refraction indices of the deposited films were found to ben0=1.50±0.05,k0=0.07±0.05,ne=1.53±0.05ke=0, optical axis being perpendicular to the surface. The values of refractivity characterize the whole film (up to seven bilayers) and do not vary with increasing thickness.