Ultrasound-induced ordering in poly(3-hexylthiophene): role of molecular and process parameters on morphology and charge transport.

Facile methods for controlling the microstructure of polymeric semiconductors are critical to the success of large area flexible electronics. Here we explore ultrasonic irradiation of solutions of poly(3-hexylthiophene) (P3HT) as a simple route to creating ordered molecular aggregates that result in a one to two order of magnitude improvement in field effect mobility. A detailed investigation of the ultrasound induced phenomenon, including the role of solvent, polymer regioregularity (RR) and film deposition method, is conducted. Absorption spectroscopy reveals that the development of low energy vibronic features is dependent on both the regioregularity as well as the solvent, with the latter especially influential on the intensity and shape of the band. Use of either higher regioregular polymer or ultrasonic irradiation of lower regioregular polymer solutions results in high field effect mobilities that are nearly independent of the dynamics of the film formation process. Surprisingly, no distinct correlation between thin-film morphology and macroscopic charge transport could be ascertained. The relationships between molecular and process parameters are very subtle: modulation of one effects changes in the others, which in turn impact charge transport on the macroscale. Our results provide insight into the degree of control that is required for the development of reproducible, robust materials and processes for advanced flexible electronics based on polymeric materials.

Hollow microneedles for intradermal injection fabricated by sacrificial micromolding and selective electrodeposition.

Limitations with standard intradermal injections have created a clinical need for an alternative, low-cost injection device. In this study, we designed a hollow metal microneedle for reliable intradermal injection and developed a high-throughput micromolding process to produce metal microneedles with complex geometries. To fabricate the microneedles, we laser-ablated a 70 µm × 70 µm square cavity near the tip of poly(lactic acid) (PLA) microneedles. The master structure was a template for multiple micromolded poly(lactic acid-co-glycolic acid) (PLGA) replicas. Each replica was sputtered with a gold seed layer with minimal gold deposited in the cavity due to masking effects. In this way, nickel was electrodeposited selectively outside of the cavity, after which the polymer replica was dissolved to produce a hollow metal microneedle. Force-displacement tests showed the microneedles, with 12 µm thick electrodeposition, could penetrate skin with an insertion force 9 times less than their axial failure force. We injected fluid with the microneedles into pig skin in vitro and hairless guinea pig skin in vivo. The injections targeted 90 % of the material within the skin with minimal leakage onto the skin surface. We conclude that hollow microneedles made by this simple microfabrication method can achieve targeted intradermal injection.

Solvent evaporation induced liquid crystalline phase in poly(3-hexylthiophene).

We report on the evolution of the chain orientation of a representative π-conjugated polymer, poly(3-hexylthiophene) (P3HT), during the solution-casting process, as monitored using polarized Raman spectroscopy. These measurements point to the formation of a liquid-crystalline phase of P3HT solutions within a specific time period during solvent evaporation, which leads to a conducting channel. These conclusions are based on the angular dependence of polarized Raman scattering peaks, the anisotropy in the fluorescence background signal, analysis of the scattering-peak shape, and direct observations of the three-phase contact line in an optical microscope under crossed polarizers. These results shed new light on the evolution of chain alignment and thus materials nanostructure, specifically in solution-processed P3HT and more generally in π-conjugated systems. They may further enable the design of improved materials and processes for this important class of polymers.

Electrical contact properties between the accumulation layer and metal electrodes in ultrathin poly(3-hexylthiophene)(P3HT) field effect transistors.

Probing contact properties between an ultrathin conjugated polymer film and metal electrodes in field effect transistors (FETs) is crucial not only to understanding charge transport properties in the accumulation layer but also in building organic sensors with high sensitivity. We investigated the contact properties between gold electrodes and poly(3-hexylthiophene) (P3HT) as a function of film thickness using gated four-point sheet resistance measurements. In an FET with a 2 nm thick P3HT film, a large voltage drop of 1.9 V (V(D) = -3 V) corresponding to a contact resistance of 2.3 × 10(8) Ω was observed. An effective FET mobility of 1.4 × 10(-3) cm(2)/(V s) was calculated when the voltage drop at the contacts was factored out, which is approximately a factor of 3 greater than the two-contact FET mobility of 5.5 × 10(-4) cm(2)/(V s). A sharp decrease in the ratio of the contact resistance to the channel resistance was observed with increasing film thickness up to a thickness of approximately 6 nm, separating a contact limited regime from a charge transport limited regime. The origin of the large contact resistance observed in the device prepared with an ultrathin P3HT film is discussed in light of results from X-ray diffraction (XRD) and atomic force microscopy (AFM) studies.