C. Daniel Frisbie

Printable ion-gel gate dielectrics for low-voltage polymer thin-film transistors on plastic.

An important strategy for realizing flexible electronics is to use solution-processable materials that can be directly printed and integrated into high-performance electronic components on plastic. Although examples of functional inks based on metallic, semiconducting and insulating materials have been developed, enhanced printability and performance is still a challenge. Printable high-capacitance dielectrics that serve as gate insulators in organic thin-film transistors are a particular priority. Solid polymer electrolytes (a salt dissolved in a polymer matrix) have been investigated for this purpose, but they suffer from slow polarization response, limiting transistor speed to less than 100 Hz. Here, we demonstrate that an emerging class of polymer electrolytes known as ion gels can serve as printable, high-capacitance gate insulators in organic thin-film transistors. The specific capacitance exceeds that of conventional ceramic or polymeric gate dielectrics, enabling transistor operation at low voltages with kilohertz switching frequencies.

Functional group imaging by chemical force microscopy

Mapping the spatial arrangement of chemical functional groups and their interactions is of significant importance to problems ranging from lubrication and adhesion to recognition in biological systems. A force microscope has been used to measure the adhesive and friction forces between molecularly modified probe tips and organic monolayers terminating in a lithographically defined pattern of distinct functional groups. The adhesive interactions between simple CH3/CH3, CH3/COOH, and COOH/COOH functional groups correlate directly with friction images of sample surfaces patterned with these groups. Thus, by monitoring the friction between a specifically functionalized tip and sample, one can produce friction images that display predictable contrast and correspond to the spatial distribution of functional groups on the sample surface. Applications of this chemically sensitive imaging technique are discussed.

Electrical Resistance of Long Conjugated Molecular Wires

The charge transport mechanism of a wire can be revealed by how its electrical resistance varies with length. We have measured the resistance and current-voltage characteristics of conjugated molecular wires ranging in length from 1 to 7 nanometers, connected between metal electrodes. We observe the theoretically predicted change in direct-current transport from tunneling to hopping as a function of systematically controlled wire length. We also demonstrate that site-specific disruption of conjugation in the wires greatly increases resistance in the hopping regime but has only a small effect in the tunneling regime. These nanoscale transport measurements elucidate the role of molecular length and bond architecture on molecular conductivity and open opportunities for greater understanding of electrical transport in conjugated polymer films.

Electrolyte‐Gated Transistors for Organic and Printed Electronics

Here we summarize recent progress in the development of electrolyte-gated transistors (EGTs) for organic and printed electronics. EGTs employ a high capacitance electrolyte as the gate insulator; the high capacitance increases drive current, lowers operating voltages, and enables new transistor architectures. Although the use of electrolytes in electronics is an old concept going back to the early days of the silicon transistor, new printable, fast-response polymer electrolytes are expanding the potential applications of EGTs in flexible, printed digital circuits, rollable displays, and conformal bioelectronic sensors. This report introduces the structure and operation mechanisms of EGTs and reviews key developments in electrolyte materials for use in printed electronics. The bulk of the article is devoted to electrical characterization of EGTs and emerging applications.

Printed, sub-3V digital circuits on plastic from aqueous carbon nanotube inks

Printing electronic components on plastic foils with functional liquid inks is an attractive approach for achieving flexible and low-cost circuitry for applications such as bendable displays and large-area sensors. The challenges for printed electronics, however, include characteristically slow switching frequencies and associated high supply voltages, which together impede widespread application. Combining printable high-capacitance dielectrics with printable high-mobility semiconductors could potentially solve these problems. Here we demonstrate fast, flexible digital circuits based on semiconducting carbon nanotube (CNT) networks and high-capacitance ion gel gate dielectrics, which were patterned by jet printing of liquid inks. Ion gel-gated CNT thin-film transistors (TFTs) with 50 microm channel lengths display ambipolar transport with electron and hole mobilities >20 cm(2)/V.s; these devices form the basis of printed inverters, NAND gates, and ring oscillators on both polyimide and SiO(2) substrates. Five-stage ring oscillators achieve frequencies >2 kHz at supply voltages of 2.5 V, corresponding to stage delay times of 50 micros. This performance represents a substantial improvement for printed circuitry fabricated from functional liquid inks.

Surface potential profiling and contact resistance measurements on operating pentacene thin-film transistors by Kelvin probe force microscopy

Surface potentials of operating pentacene thin-film transistors (TFTs) with two different contact geometries (bottom or top) were mapped by Kelvin probe force microscopy (KFM). The surface potential distribution was used to isolate the potential drops at the source and drain contacts. These potential drops were converted to resistances by dividing by the appropriate drain current values. The bottom contact TFTs were contact limited at large gate voltages, while the top contact TFTs were not contact limited. In both geometries, the contact and the channel resistances decreased strongly with increasing (negative) gate bias but did not depend strongly on the drain bias. This study demonstrates the utility of KFM for visualizing charge transport bottlenecks in operating pentacene devices and for correlating electrical behavior with device structure by comparison of surface potential and topographic maps.

Gated four-probe measurements on pentacene thin-film transistors: Contact resistance as a function of gate voltage and temperature

We describe gated four-probe measurements designed to measure contact resistance in pentacene-based organic thin-film transistors (OTFTs). The devices consisted of metal source and drain electrodes contacting a 300-A-thick pentacene film thermally deposited on Al2O3 or SiO2 dielectrics with a p-doped Si substrate serving as the gate electrode. Voltage-sensing leads extending into the source-drain channel were used to monitor potentials in the pentacene film while passing current during drain voltage (VD) or gate voltage (VG) sweeps. We investigated the potential profiles as a function of contact metallurgy (Pt, Au, Ag, and Ca), substrate chemistry, VG, and temperature. The contact-corrected linear hole mobilities were as high as 1.75cm2∕Vs and the film sheet resistance and specific contact resistance were as low as 600kΩ∕◻ and 1.3kΩ-cm, respectively, at high gate voltages. In the temperature range of 50–200K, the pentacene OTFTs displayed an activated behavior with activation energies of 15–30meV. Importa...

Measuring relative barrier heights in molecular electronic junctions with transition voltage spectroscopy.

Though molecular devices exhibiting potentially useful electrical behavior have been demonstrated, a deep understanding of the factors that influence charge transport in molecular electronic junctions has yet to be fully realized. Recent work has shown that a mechanistic transition occurs from direct tunneling to field emission in molecular electronic devices. The magnitude of the voltage required to enact this transition is molecule-specific, and thus measurement of the transition voltage constitutes a form of spectroscopy. Here we determine that the transition voltage for a series of alkanethiol molecules is invariant with molecular length, while the transition voltage of a conjugated molecule depends directly on the manner in which the conjugation pathway has been extended. Finally, by examining the transition voltage as a function of contact metal, we show that this technique can be used to determine the dominant charge carrier for a given molecular junction.

Electronic Impurity Doping in CdSe Nanocrystals

We dope CdSe nanocrystals with Ag impurities and investigate their optical and electrical properties. Doping leads not only to dramatic changes but surprising complexity. The addition of just a few Ag atoms per nanocrystal causes a large enhancement in the fluorescence, reaching efficiencies comparable to core-shell nanocrystals. While Ag was expected to be a substitutional acceptor, nonmonotonic trends in the fluorescence and Fermi level suggest that Ag changes from an interstitial (n-type) to a substitutional (p-type) impurity with increased doping.

“Cut and Stick” Rubbery Ion Gels as High Capacitance Gate Dielectrics

A free-standing polymer electrolyte called an ion gel is employed in both organic and inorganic thin-film transistors as a high capacitance gate dielectric. To prepare a transistor, the free-standing ion gel is simply laid over a semiconductor channel and a side-gate electrode, which is possible because of the gels high mechanical strength.