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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.

Graphene, an atomically thin two-dimensional carbonaceous material, has attracted tremendous attention in the scientific community, due to its exceptional electronic, electrical, and mechanical properties. Indeed, with the recent explosion of methods for a large-scale synthesis of graphene, the number of publications related to graphene and other graphene based materials has increased exponentially. Particularly the development of easy preparation methods for graphene like materials, such as highly reduced graphene oxide (HRG) via reduction of graphite oxide (GO), offers a wide range of possibilities for the preparation of graphene based inorganic nanocomposites by the incorporation of various functional nanomaterials for a variety of applications. In this review, we discuss the current development of graphene based metal and metal oxide nanocomposites, with a detailed account of their synthesis and properties. Specifically, much attention has been given to their wide range of applications in various fields, including electronics, electrochemical and electrical fields. Overall, by the inclusion of various references, this review covers in detail the aspects of graphene-based inorganic nanocomposites.

In this paper, we very briefly review DNA biosensors based on optical and electrical detection principles, referring mainly to our past work applying both techniques but here using nearly identical sensor chip surface architectures, i.e., capture probe layers that were prepared based on a pulsed plasma deposition protocol for maleic anhydride and subsequent wet-chemical attachment of the amine-functionalized peptide nucleic acid (PNA) probe oligonucleotides. 15 mer DNA target strands, labeled with Cy5-chromophores that were attached at the 5’ end were used for surface plasmon optical detection and the same target DNA but without label was used in OTFT sensor-based detection where the mere charge density of the bound (hybridized) DNA molecules modulate the source-drain current. The sensing mechanisms and the detection limits of the devices are described in some detail. Both techniques allow for the monitoring of surface hybridization reactions, and offer the capacity to quantitatively discriminate between targets with different degrees of mismatched sequences.

Spin-coating is currently the most widely used solution processing method in organic electronics. Here, we report, for the first time, a direct investigation of the formation process of the small-molecule organic semiconductor (OSC) 6,13-bis(triisopropylsilylethynyl) (TIPS)-pentacene during spin-coating in the context of an organic thin film transistor (OTFT) application. The solution thinning and thin film formation were monitored in situ by optical reflectometry and grazing incidence wide angle X-ray scattering, respectively, both of which were performed during spin-coating. We find that OSC thin film formation is akin to a quenching process, marked by a deposition rate of ∼100 nm s−1, nearly three orders of magnitude faster than drop-casting. This is then followed by a more gradual crystallization and healing step which depends upon the spinning speed. We associate this to further crystallization and healing of defects by residency of the residual solvent trapped inside the kinetically trapped film. The residency time of the trapped solvent is extended to several seconds by slowing the rotational speed of the substrate and is credited with improving the carrier mobility by nearly two orders of magnitude. Based on this insight, we deliberately slow down the solvent evaporation further and increase the carrier mobility by an additional order of magnitude. These results demonstrate how spin-coating conditions can be used as a handle over the crystallinity of organic semiconductors otherwise quenched during initial formation only to recrystallize and heal during extended interaction with the trapped solvent.

The infl uence of polymer entanglement on the self-assembly, molecular packing structure, and microstructure of low- M w (lightly entangled) and high- M w (highly entangled) poly (3-hexylthiophene) (P3HT), and the carrier transport in thin-fi lm transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self-assembly of well-ordered and highly textured fi brils at the solid‐liquid interface. In low- M w P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high- M w P3HT solutions increases carrier mobility up to ≈ 20-fold, by enhancing interchain and intrachain ordering while maintaining a suffi ciently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high- M w P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low- M w P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport.

The potential of pulsed plasma deposited polyallylamine (PAA) adlayer has been successfully demonstrated for fabrication of polypeptide brushes functionalized soft flexible polymeric surfaces. Polymeric substrates functionalized with the plasma deposition PAA adlayer resulted in polymeric surfaces functionalized with amino groups, which are the suitable initiating moieties for ring-opening polymerization (ROP) of N-carboxy anhydride of benzyl- l -glutamate (NCA-BLG) monomer. Poly(γ-benzyl- l -glutamate) (PBLG) brushes were grown on PAA functionalized polypropylene (PP), and polytetrafluoroethylene (PTFE) polymeric substrates. These substrates were intentionally chosen for their inert chemical nature towards most wet chemical surface modification reactions. Surface grafted thin films of poly(γ-benzyl- l -glutamate) PBLG on both the PP and PTFE polymeric substrates yielded high density PBLG brushes. PBLG chain orientation, secondary structure and grafting density were characterized by infra-red spectroscopy. The synthesis of PBLG brushes on a flexible polymeric substrate is unprecedented and technologically important, since PBLG possess good electro-optical activity. Analysis of brush layers by Attenuated Total Reflectance Infra-Red (ATR-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) as well as atomic force microscopy (AFM) fully corroborated the success of the plasma activated soft surface grafting approach.

Blending of small-molecule organic semiconductors (OSCs) with amorphous polymers is known to yield high performance organic thin film transistors (OTFTs). Vertical stratification of the OSC and polymer binder into well-defined layers is crucial in such systems and their vertical order determines whether the coating is compatible with a top and/or a bottom gate OTFT configuration. Here, we investigate the formation of blends prepared via spin-coating in conditions which yield bilayer and trilayer stratifications. We use a combination of in situ experimental and computational tools to study the competing effects of formulation thermodynamics and process kinetics in mediating the final vertical stratification. It is shown that trilayer stratification (OSC/polymer/OSC) is the thermodynamically favored configuration and that formation of the buried OSC layer can be kinetically inhibited in certain conditions of spin-coating, resulting in a bilayer stack instead. The analysis reveals here that preferential loss of the OSC, combined with early aggregation of the polymer phase due to rapid drying, inhibit the formation of the buried OSC layer. The fluid dynamics and drying kinetics are then moderated during spin-coating to promote trilayer stratification with a high quality buried OSC layer which yields unusually high mobility >2 cm2 V−1 s−1 in the bottom-gate top-contact configuration.

The authors are grateful to Mr. Mohammed Balamesh for his important contributions to the operational readiness of the Organic Electronics and Photovoltaics Laboratory at King Abdullah University of Science and Technology, where most of this work was performed. Part of this work was supported by KAUST's Office of Competitive Research Funds under award number FIC/2010/04. The authors acknowledge use of the D1 beam line at the Cornell High Energy Synchrotron Source supported by the National Science Foundation (NSF DMR-0225180) and NIH-NIGMS.

Organic electronics are beginning to attract more interest for biosensor technology as they provide an amenable interface between biology and electronics. Stable biosensor based on electronic detection platform would represent a significant advancement in technology as costs and analysis time would decrease immensely. Organic materials provide a route toward that goal due to their compatibility with electronic applications and biological molecules. In this report, we detail the effects of experimental parameters, such as pH and concentration, toward the selective detection of DNA via surface-bound peptide nucleic acid (PNA) sequences on organic transistor biosensors. The OTFT biosensors are fabricated with thin-films of the organic semiconductor, 5,5′-bis-(7-dodecyl-9H-fluoren-2-yl)-2,2′-bithiophene (DDFTTF), in which they exhibit a stable mobility of 0.2 cm2 V−1 s−1 in buffer solutions (phosphate-buffer saline, pH 7.4 or sodium acetate, pH 7). Device performance were optimized to minimize the deleterious effects of pH on gate–bias stress such that the sensitivity toward DNA detection can be improved. In titration experiments, the surface-bound PNA probes were saturated with 50 nM of complementary target DNA, which required a 10-fold increase in concentration of single-base mismatched target DNA to achieve a similar surface saturation. The binding constant of DNA on the surface-bound PNA probes was determined from the concentration-dependent response (titration measurements) of our organic transistor biosensors.

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.

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 SiO2 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.

Organic thin-film transistors show tremendous potential for versatile electronic sensors. Critical challenges facing the integration of organic thin-film transistors (OTFTs) as chemical and biological sensors include reproducibility, sensitivity, and particularly stability. Here, we describe a bilayer organic semiconductor structure consisting of a pentacene active layer with copper phthalocyanine as the top surface passivation layer. In this architecture, the copper phthalacyanine (CuPc) acts as a surface passivation layer with efficient charge injection into the pentacene layer, thus providing a versatile method for the incorporation of many semiconductor materials as the sensing element. OTFTs fabricated with the described structure exhibited a field-effect mobility of 1.15 ± 0.2 cm2 V−1 s−1 at −2 V in ambient conditions with stable performance in aqueous media (0.5 cm2 V−1 s−1 at −1 V). X-ray diffraction (XRD) confirms that the bilayer film achieves a high degree of molecular order as suggested by the...

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.

International audience; In this short review, we summarize the design and implementation of organic semiconducting materials-based field-effect transistors (OFETs) and the fabrication and use of reduced graphene-oxide field-effect transistors (rGO–FETs) as flexible transducers for electronic biosensing. We demonstrate that these platforms allow for the quantitative, in situ, and in real time monitoring of bio-affinity reactions between analytes from solution to the surface-immobilized receptors. The examples given include the binding of anti-bovine serum albumin (BSA) antibodies to their antigen, BSA, covalently attached to the channel of an OFET, or the reverse mode of operation, i.e., the binding of BSA from solution to the antibodies immobilized on a rGO transistor. Finally, we will discuss a few results obtained with odorant binding proteins used as receptors on a rGO–FET transducer for the realization of a biomimetic smell sensor

We demonstrate a new way to investigate and control the solvent vapor annealing of solution-cast organic semiconductor thin films. Solvent vapor annealing of spin-cast films of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn) is investigated in situ using quartz crystal microbalance with dissipation (QCM-D) capability, allowing us to monitor both solvent mass uptake and changes in the mechanical rigidity of the film. Using time-resolved grazing incidence wide angle X-ray scattering (GIWAXS) and complementary static atomic force microscopy (AFM), we demonstrate that solvent vapor annealing in the molecular regime can cause significant performance improvements in organic thin film transistors (OTFTs), whereas allowing the solvent to percolate and form a liquid phase results in catastrophic reorganization and dewetting of the film, making the process counterproductive. Using these lessons we devise processing conditions which prevent percolation of the adsorbed solvent vapor molecules for extended periods, thus extending the benefits of solvent vapor annealing and improving carrier mobility by nearly two orders of magnitude. Ultimately, it is demonstrated that QCM-D is a very powerful sensor of the state of the adsorbed solvent as well as the thin film, thus making it suitable for process development as well as in-line process monitoring both in laboratory and in future manufacturing settings.

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.

A chemically specific and facile method for growth of ZnO nanorods on WS2 nanotubes (NT-WS2) is reported. The modification strategy is based on the chalcophilic affinity of Zn, which serves as an anchor to immobilize ZnO colloids onto the WS2 nanotubes. The surface bound ZnO colloids have been used as a seed to grow ZnO nanorods on WS2 nanotubes. The immobilization of ZnO colloids was monitored by UV−vis spectroscopy and photoluminescence spectroscopy whereas the growth of ZnO nanorods was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Linear and non-linear dynamic properties of a re-entrant ferromagnetic polycrystalline bulk La0.85Ca0.15Mn0.95Fe0.05O3 sample are studied using AC susceptibility. This sample composition shows a transition from paramagnetic (PM) to ferromagnetic (FM) at around 174 K and to spin glass (SG) at ~100 K. The dynamic behaviour is investigated in the intermediate temperature range (Tg