Carrier Transport Enhancement in Conjugated Polymers through Interfacial Self-Assembly of Solution-State Aggregates.

We demonstrate that local and long-range orders of poly(3-hexylthiophene) (P3HT) semicrystalline films can be synergistically improved by combining chemical functionalization of the substrate with solution-state disentanglement and preaggregation of P3HT in a θ solvent, leading to a very significant enhancement of the field effect carrier mobility. The preaggregation and surface functionalization effects combine to enhance the carrier mobility nearly 100-fold as compared with standard film preparation by spin-coating, and nearly 10-fold increase over the benefits of preaggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of preaggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to unaggregated polymer chains in the same conditions. Additional measurements reveal the combined preaggregation and surface functionalization significantly enhances local order of the conjugated polymer through planarization and extension of the conjugated backbone of the polymer which clearly translate to significant improvements of carrier transport at the semiconductor-dielectric interface in organic thin film transistors. This study points to opportunities in combining complementary routes, such as well-known preaggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

Surface initiated polymerization on pulsed plasma deposited polyallylamine: a polymer substrate-independent strategy to soft surfaces with polymer brushes.

The deposition of polyallylamine (PAA) adlayers by pulsed plasma polymerization on various types of polymeric substrates has been explored as a general route to amino functionalized polymeric surfaces. These amino groups are highly suitable for anchoring an atom transfer radical polymerization (ATRP) initiator via a robust amide linkage. Subsequent surface initiated ATRP (SI-ATRP) of monomethoxy oligo(ethylene glycol) methacrylate (MeOEGMA) resulted in polyMeOEGMA brush grafted polymer surfaces. This combined strategy of pulsed plasma polymerization with SI-ATRP was demonstrated for five different polymeric substrates namely polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyimide (PI), polypropylene (PP), and polytetrafluoroethylene (PTFE). Analysis of brush layers by attenuated total reflection infrared (ATR-IR) spectroscopy as well as X-ray photoelectron spectroscopy (XPS) fully corroborated the success of the proposed strategy for all substrate types.

Effect of passivation on the sensitivity and stability of pentacene transistor sensors in aqueous media.

Charge-detecting biosensors have recently become the focal point of biosensor research, especially research onto organic thin-film transistors (OTFTs), which combine compactness, a low cost, and fast and label-free detection to realize simple and stable in vivo diagnostic systems. We fabricated organic pentacene-based bottom-contact thin-film transistors with an ultra-thin insulating layer of a cyclized perfluoro polymer called CYTOP (Asahi Glass Co., Tokyo, Japan) on SiO(2) for operation in aqueous media. The stability and sensitivity of these transistor sensors were examined in aqueous buffer media with solutions of variable pH levels after the passivation of perfluoro polymers with thicknesses ranging from 50 to 300 nm. These transistor sensors were further modified with an ultra-thin film (5 nm) functional layer for selective BSA/antiBSA detection in aqueous buffer media, demonstrating a detection capability as low as 500 nM of concentrated antiBSA. The dissociation constant from the antiBSA detection results was 2.1×10(-6)M. Thus, this study represents a significant step forward in the development of organic electronics for a disposable and versatile chemical and bio-sensing platform.

In situ antibody detection and charge discrimination using aqueous stable pentacene transistor biosensors.

Pentacene-based organic thin-film transistors were used to create highly sensitive, real-time electronic sensors for selective antibody detection. Bovine serum albumin was covalently attached to a modified pentacene surface to selectively detect the label free monoclonal antiBSA. These sensors displayed a high affinity constant (K(A)) of (1.1 ± 3) × 10(7) M(-1) at pH 7, which is 1 order of magnitude higher than those obtained with a highly sensitive surface plasmon resonance spectroscopy detection system. Furthermore, a high degree of discrimination in the hybrid antiBSA charges was achieved at different pH values. This demonstration of fast, label-free, real-time detection of nanoscale biomolecules in aqueous buffer solutions using the organic transistor sensing platform will have a significant impact on high-performance microarrays in addition to discriminating the presence of ionizable groups.