Incorporation of Poly(TFEMA) in Perovskite Thin Films Using a Supercritical Fluid.

A new process is reported for the incorporation of a fluoropolymer into a solid perovskite film. Poly(trifluoroethyl methacrylate) [CH2C(CH3)(CO2CH2CF3)]n was delivered to methylammonium lead iodide (CH3NH3PbI3) perovskite films by crystallizing the film in supercritical carbon dioxide/ethanol containing the dissolved fluoropolymer. The surface was characterized before and after fluoropolymer exposure using scanning electron microscopy, Raman spectroscopy, and contact angle measurements. The results indicate that the fluoropolymer was incorporated into the perovskite film during the supercritical fluid crystallization process. The incorporation of a hydrophobic fluoropolymer into perovskite has the potential to improve resistance to environmental degradation.

Moisture Stability of Perovskite Solar Cells Processed in Supercritical Carbon Dioxide.

Performance degradation under environmental conditions currently limits the practical utility of perovskite-based solar cells. The moisture stability of CH3NH3PbI3 perovskite films and solar cells was measured during exposure to three different levels of relative humidity. The films were crystallized at two different temperatures with and without simultaneous exposure to supercritical carbon dioxide. The film crystallinity, optical absorption, and device photoconversion efficiency was measured over time for three relative humidity levels and both crystallization methods. It was determined that film crystallization in supercritical CO2 resulted in significant improvement in moisture stability for films processed at 50 °C, but negligible improvement in stability for films processed at 100 °C.

The Effect of Cations on Uranyl Transport and Fluorescence in Mesoporous Silica Gel.

The fluorescence intensity and transport kinetics of uranyl into mesoporous silica gel was measured in the presence of six naturally occurring cations. It was shown that the presence of the cations can reduce the fluorescence intensity of the uranyl through collision quenching and through competition for the silica gel surface sites. Stern-Volmer quenching coefficients were obtained by measuring the uranyl fluorescence as a function of cation concentration. The cations compete with uranyl to occupy silica gel surface sites and cause a decrease in uranyl fluorescence intensity and a reduction in the uranyl saturation time constant. Energy-dispersive x-ray spectroscopy (EDS) was used to measure the weight percentage of uranium and the cations in the silica gel samples and these results correlated well with the results of the saturation time constant measurements. The results of this study show that, at high concentrations, the presence of cations in water can influence the fluorescence intensity and transport kinetics of uranyl into mesoporous silica gel.

In situ, noninvasive characterization of superhydrophobic coatings.

Light scattering was used to measure the time-dependent loss of air entrapped within a submerged microporous hydrophobic surface subjected to different environmental conditions. The loss of trapped air resulted in a measurable decrease in surface reflectivity and the kinetics of the process was determined in real time and compared to surface properties, such as porosity and morphology. The light-scattering results were compared with measurements of skin-friction drag, static contact angle, and contact-angle hysteresis. The in situ, noninvasive optical technique was shown to correlate well with the more conventional methods for quantifying surface hydrophobicity, such as flow slip and contact angle.

Wetting behavior of polymer coated nanoporous anodic alumina films: transition from super-hydrophilicity to super-hydrophobicity.

We show that nanoporous anodic alumina films, with pore diameters in the range 10-80 nm, can be transformed from being very hydrophilic (or super-hydrophilic) to very hydrophobic (or super-hydrophobic) by coating the surface with a thin (2-3 nm) layer of a hydrophobic polymer. This dramatic transformation happens as a result of the interplay between surface morphology and surface chemistry. The coated surfaces exhibit 'sticky' hydrophobicity as a result of ingress of water into the pores by capillary action. The wetting parameters (contact angle and contact angle hysteresis) exhibit qualitatively different dependences on pore diameters in coated and uncoated films, which are explained by invoking appropriate models for wetting.

Uranyl soil extraction and fluorescence enhancement by nanoporous silica gel: pH effects.

Nanoporous silica gel was employed to extract uranyl from contaminated soil and to enhance the fluorescence intensity and lifetime. The fluorescence lifetime and intensity of uranyl ions absorbed within nanoporous silica gel was measured from pH 1-13. The results show that the uranyl fluorescence intensity can be enhanced by approximately two orders of magnitude by the silica nanoporous matrix from pH 4-12 with the greatest enhancement occurring from pH 4-7. The enhanced fluorescence lifetime can be used in time-gated measurements to help minimize the influence of background environmental fluorophores.

Fluorescence resonance energy transfer based MCM-EDTA-Tb3+-MES sensor.

An in situ mesopourous surface imprinted polymeric (SIP) sensor was synthesized for a highly sensitive, selective, and kinetically faster detection of the high-vapor-pressure nerve gas surrogate methyl salicylate (MES). Visual detection occurred on the filtrate thin films at 25 pM. Other nerve gas surrogates, TP, DMP, DMMP, PMP, and 1,4-thioxane, were tested and showed a decrease in sensitivity compared to MES. In addition, 2,6-dipicolinic acid (DPA), a biological indicator, was also investigated and showed a decrease in sensitivity compared to MES. Finally, the detection plateau was reached at 40 s and at 1.5 x 10(-4) M from pH 6-11.

Organic zeolites from a diolefinic monomer.

Submicrometer particles of diethyl p-phenylenediacrylate (EPA) with tunable molecular adsorption characteristics were produced by solid-state photopolymerization in the presence of template molecules. EPA monomer particles were produced by rapid expansion of supercritical solutions (RESS), and deposited directly onto surface acoustic wave (SAW) resonators. The EPA particles were photopolymerized directly on the SAW devices in the presence of molecular templates, and dynamic sorption isotherms of C1- through C9-alkanes were studied to characterize the particle-vapor interaction. The mass increase due to vapor uptake into the particulate coatings was measured by monitoring the SAW resonance frequency during vapor sorption. The vapor selectivity and molecular porosity of the particulate coatings were studied in situ on the piezoelectric substrate by measuring sorption isotherms. A gradual exclusion of smaller alkane molecules from the molecularly imprinted particulate coatings was observed with decreasing template molecule size. The observed selective and reversible adsorption of alkane analytes with different molecular sizes suggest that these imprinted polymers may be categorized as organic analogues of zeolites.

Steady-state and frequency-domain lifetime measurements of an activated molecular imprinted polymer imprinted to dipicolinic acid.

We recently demonstrated the synthesis and fluorescence activity associated with an optical detector incorporating a molecular imprinted polymer (MIP). Steady-state and time-resolved (lifetime) fluorescence measurements were used to characterize the binding activity associated with MIP microparticles imprinted to dipicolinic acid (DPA). DPA is a unique biomarker associated with the sporulation phase of endospore-forming bacteria. Vinylic monomers were polymerized in a dimethylformamide solution containing DPA as a template. The resulting MIP was then pulverized and sorted into small microscale particles. Tests were conducted on replicate samples of biologically active cultures representing both vegetative stationary phase and sporulation phase of Bacillus subtilis in standard media. Samplers were adapted incorporating the MIP particles within a dialyzer cartridge (500 MW). The permeability of the dialyzer membrane permitted diffusion of lighter molecular weight constituents from microbial media effluents to enter the dialyzer chamber and come in contact with the MIP. Results showed dramatic (10-fold over background) steady-state fluorescence changes (as a function of excitation, emission and intensity) for samples associated with high endospore biomass (DPA), and a frequency-domain lifetime of 5.3 ns for the MIP-DPA complex.