Tuning optical properties of poly(3-hexylthiophene) nanoparticles through hydrothermal processing

Abstract

Poly(3-hexylthiophene) (P3HT) nanoparticles (NPs) were prepared by a reprecipitation method. Hydrothermal processing applied external pressure to the pristine P3HT NPs at temperatures ranging from 60 to 150 °C. Optical absorption and photoluminescence (PL) spectra for the hydrothermally treated P3HT NPs varied markedly with the processing temperature. With increasing treatment temperature, the absorption peak broadened and the peak position shifted from 510 to 623 nm; moreover, the intensity ratio of the 0–1 to 0–0 emission varied. These changes were caused by interactions between the P3HT main chains and alkyl side groups and conformational modifications induced by the high pressure during the hydrothermal process. The evolution of the optical absorption spectra of the P3HT NPs during the hydrothermal processing was strongly correlated with the variation of PL excitation spectra and with the PL emission spectra of a single NP.     

Tuning optical properties of poly(3-hexylthiophene) nanoparticles through hydrothermal processing

Poly(3-hexylthiophene) (P3HT) nanoparticles (NPs) were prepared by a reprecipitation method. Hydrothermal processing applied external pressure to the pristine P3HT NPs at temperatures ranging from 60 to 150 °C. Optical absorption and photoluminescence (PL) spectra for the hydrothermally treated P3HT NPs varied markedly with the processing temperature. With increasing treatment temperature, the absorption peak broadened and the peak position shifted from 510 to 623 nm; moreover, the intensity ratio of the 0–1 to 0–0 emission varied. These changes were caused by interactions between the P3HT main chains and alkyl side groups and conformational modifications induced by the high pressure during the hydrothermal process. The evolution of the optical absorption spectra of the P3HT NPs during the hydrothermal processing was strongly correlated with the variation of PL excitation spectra and with the PL emission spectra of a single NP.     

Transport study of a novel polyfluorene/poly(p-phenylenevinylene) copolymer by various mobility models

The polyfluorene/poly(p-phenylenevinylene) copolymer based hole-only devices are fabricated and the current–voltage characteristics are measured as a function of temperature. The hole current is fitted well with space-charge limited and field-dependent mobility model, which provides a direct measurement of the hole mobility μ as a function of electric field E and temperature. The mobility is fitted with existing Gill’s model, Gaussian disorder model, correlated Gaussian disorder model and Brownian motion model. Energy hopping time and activation energy are obtained from Brownian motion model. Microscopic transport parameters are derived and a consistent picture of the influence of the molecular structure of the polymer on the charge transport is depicted. For the polyfluorene/poly(p-phenylenevinylene) copolymer, although with a high degree of irregularity in structure and larger energetic disorder, the two bulky structure favors charge delocalization and remove defect sites, results in a higher mobility. The results suggest space-charge limited and field-dependent mobility model combine with various mobility model, include Brownian motion model, is a useful technique to study charge transport in thin films with thicknesses close to those used in real devices.     

In situ synthesis and optical limiting response of poly(N-vinylcarbazole) functionalized single-walled carbon nanotubes

A new poly(N-vinylcarbazole)-covalently grafted single-wall carbon nanotube (SWNT-PVK) hybrid material was synthesized by an in situ anionic polymerization reaction of N-vinylcarbazole and the negatively charged SWNTs. Incorporation of the PVK moieties onto the SWNTs' surface considerably improves the solubility and processability of SWNTs. At the same level of linear transmission, the SWNT-PVK dispersions show better optical limiting performance than the pristine SWNT dispersions, which shows this material to be a suitable candidate for viable optical limiting devices. Micro-plasma and/or micro-bubble induced nonlinear scattering is considered as the main mechanism for optical limiting.     

Large nonlocal nonlinear optical response of castor oil

The nonlocal nonlinearity of castor oil was investigated using the Z-scan technique in the CW regime at 514 nm and in femtosecond regime at 810 nm. Large negative nonlinear refractive indexes of thermal origin, thermo-optical coefficients and degree of nonlocality were obtained for both laser excitation wavelengths. The results indicate that the electronic part of the nonlinear refractive index and nonlinear absorption were negligible. Our results suggest that castor oil is promising candidate as a nonlinear medium for several nonlocal optical applications, such as in spatial soliton propagation, as well as a dispersant agent in the measurement of absorptive properties of nanoparticles.     

Giant electrostrictive response in poly(vinylidene fluoride-hexafluoropropylene) copolymers

Electrostrictive strains were measured in three different polymeric materials: a low modulus polyurethane elastomer, previously studied by Scheinbeim et al. (1994), and two higher modulus random copolymers of poly(vinylidene fluoride-hexafluoropropylene) [P(VDF-HFP)] with 5% and 15% HFP content. Measurements at increasing voltage (electric fields ranging from 0 to 60 MV/m) were taken using an air gap capacitance system and then converted to sample thickness. Copolymer samples with different thermal histories were compared, ice water quenched, air quenched, and slow cooled, for both compositions. The ice water-quenched 5% P(VDF-HFP) copolymer exhibited the highest strain response (>4%) with a dielectric constant of 13.9. The previously studied polyurethane elastomer exhibited the second highest strain response, >3%, with the lowest dielectric constant, 8.5. The ice water-quenched 15% HFP copolymer exhibited the lowest strain response among the three polymeric materials tested, /spl ap/3%, with a dielectric constant of 12.2. The strain energy density of the 5% HFP ice water-quenched copolymer, /sup 1///sub 2/ YS/sub m//sup 2/ (/sup 1///sub 2/ Young's modulus, Y, times the maximum electrostrictive strain, S/sub max/ squared), is the largest known for any semi-crystalline polymer: 0.88J/cm/sup 3/.     

Potentiometric response characteristics of polycation-sensitive membrane electrodes toward poly(amidoamine) and poly(propylenimine) dendrimers

The potentiometric response characteristics of polycation-sensitive membrane electrodes toward two classes of polycationic dendrimers are examined. Using appropriately formulated polymer membrane electrodes composed of a dinonylnaphthalenesulfonate (DNNS) salt in a plasticized polyurethane matrix, it is shown that poly(amidoamine) (PAMAM) and poly(propylenimine) (PPI) dendrimers are readily detected at submicrogram per milliliter levels via a nonequilibrium response mechanism. The relationship between the total EMF response (at equilibrium) and the specific dendrimer structure is also examined. For both the PAMAM and PPI species, it is shown that the total EMF response does not change significantly with dendrimer generation number; however, the nonequilibrium analytically useful response curves are shifted to higher mass concentrations as the generation number is increased. The relative contributions of the terminal primary amines and the interior tertiary amines of the dendrimers to the observed EMF response are investigated by synthesis of various dendrimer derivatives (acetylated, quaternized, etc.). By comparing the total EMF responses for these derivatives as a function of sample pH, it is demonstrated that the lipophilic cation exchanger (DNNS) within the membrane phase can likely interact electrostatically with both protonated forms of the terminal primary amines and interior tertiary amines of the dendrimer structures. The practical application of the nonequilibrium potentiometric detection of dendrimers for monitoring their interaction with DNA is also demonstrated.     

Preparation and optical properties of a poly(N-vinylcarbazole) material

We report on the photorefractive properties of a stable polymeric material based on the host polymer, poly(N-vinylcarbazole). Two-beam coupling and four-wave mixing experiments were used to measure the performance of devices constructed by sandwiching the material, composed of host, plasticizer, photo-sensitizer, and non-linear optical chromophore, between transparent electrodes. A steady-state diffraction efficiency of 60% and a two-beam coupling gain of 22 cm^–1 in excess of the absorption of 4 cm^–1 were observed at the laser's operating wavelength of 670 nm. The devices are easily prepared and have lifetimes in excess of one year with no indication of degradation when stored at ambient temperatures.     

Structural changes during photodegradation of poly(ethylene terephthalate)

An investigation has been conducted into the effects of photodegradation on the structure of poly(ethylene terephthalate) (PET). Films, with and without ultraviolet absorbers and prepared by biaxial orientation after extrusion, have been exposed in the laboratory for periods of up to 1020 hours. The samples were investigated by differential scanning calorimetry (DSC), X-ray diffraction and size exclusion chromatography. The appearance of a cold crystallization peak during DSC heating scans was noted for exposed samples and this was considered to be a result of released molecules in the amorphous region that could rearrange into a crystalline phase. From X-ray analysis, a loss of crystalline orientation was observed after degradation and an interpretation was given based on relaxation in the mesophase region. In samples containing the photostabilizer additive the magnitude of changes in structure was lower, possibly due to segregation effects during film production making the non-crystalline region relatively immune to degradation effects.     

Resistive switching induced by metallic filaments formation through poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate)

We report the design and fabrication of Al/poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/Cu resistive memory devices that utilize the Cu redox reaction and conformational features of PEDOT:PSS to achieve resistive switching. The top Cu electrode acts as the source of the redox ions that are injected through the PEDOT:PSS layer during the forming process. The Cu filament is confirmed directly using the cross-sectional images of transmission electron microscopy and energy-dispersive X-ray spectroscopy. The resultant resistive memory devices can operate over a small voltage range, i.e., the switching-on threshold voltage is less than 1.5 V and the absolute value of the switching-off threshold voltage is less than 1.0 V. The on/off current ratio is as large as 1 × 10(4) and the two different resistance states can be maintained over 10(6) s. Moreover, the devices present good thermal stability that the resistive switching can be observed even at temperature up to 160 °C, at which the oxidation of the Cu top electrode is the failure factor. Furthermore, the cause of failure for Al/PEDOT:PSS/Cu memory devices at higher temperature is confirmed to be the oxidation of Cu top electrode.     

Beam-induced changes in the scanning electron microscopy of poly(oxymethylene)

Samples of injection-moulded Delrin of a particular known morphology were examined in the scanning electron microscope. It was found that the beam affected the specimen in certain characteristic ways, the raster leaving a permanent imprint on the sample surface. By considering the nature of the irradiation process in the scanning electron microscope the amount and type of beam damage could be quantitatively correlated with the operating variables of the instrument. It is hoped that this will provide the groundwork for similar investigations on other systems. The importance of understanding and controlling beam-induced effects in the interpretation of scanning electron microscope images is clearly brought out by the present study. The nature of the beam damage bears a relation to the texture of the sample as inferred by other means. Thus the scanning electron microscope can serve as a device for achieving controlled beam etching in service of structure studies. Delrin is a poly(oxymethylene) manufactured by Du Pont de Nemours and Co. Inc.