Polymer Electrolyte Gate Research Articles

Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor

The recent discovery of graphene has led to many advances in two-dimensional physics and devices. The graphene devices fabricated so far have relied on SiO(2) back gating. Electrochemical top gating is widely used for polymer transistors, and has also been successfully applied to carbon nanotubes. Here we demonstrate a top-gated graphene transistor that is able to reach doping levels of up to 5x1013 cm-2, which is much higher than those previously reported. Such high doping levels are possible because the nanometre-thick Debye layer in the solid polymer electrolyte gate provides a much higher gate capacitance than the commonly used SiO(2) back gate, which is usually about 300 nm thick. In situ Raman measurements monitor the doping. The G peak stiffens and sharpens for both electron and hole doping, but the 2D peak shows a different response to holes and electrons. The ratio of the intensities of the G and 2D peaks shows a strong dependence on doping, making it a sensitive parameter to monitor the doping.

Phonon Softening in Individual Metallic Carbon Nanotubes due to the Kohn Anomaly

We have studied the line shape and frequency of the G band Raman modes in individual metallic single walled carbon nanotubes (M-SWNTs) as a function of Fermi level (epsilonF) position, by tuning a polymer electrolyte gate. Our study focuses on the data from M-SWNTs where explicit assignment of the G- and G+ peaks can be made. The frequency and line shape of the G- peak in the Raman spectrum of M-SWNTs is very sensitive to the position of the Fermi level. Within +/- variant Planck's over 2piomega/2 (where variant Planck's over 2piomega is the phonon energy) around the band crossing point, the G- mode is softened and broadened. In contrast, as the Fermi level is tuned away from the band crossing point, a semiconductinglike G band line shape is recovered both in terms of frequency and linewidth. Our results confirm the predicted softening of the A-symmetry LO phonon mode frequency due to a Kohn anomaly in M-SWNTs.

Vibrational Spectroscopy Reveals Electrostatic and Electrochemical Doping in Organic Thin Film Transistors Gated with a Polymer Electrolyte Dielectric

We apply attenuated total internal reflection Fourier transform infrared (ATR-FTIR) spectroscopy to directly probe active layers in organic thin film transistors (OTFTs). The OTFT studied uses the n-type organic semiconductor N-N'-dioctyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C8) and a polymer electrolyte gate dielectric made from poly(ethylene oxide) and LiClO4. FTIR spectroscopy of the device shows signatures of anionic PTCDI-C8 species and broad polaron bands when the organic semiconductor layer is doped under positive gate bias (VG). There are two distinctive doping regions: a reversible and electrostatic doping region for VG <or= 2 V and an irreversible and electrochemical doping regime for VG>2 V. On the basis of intensity loss of vibrational peaks attributed to neutral PTCDI-C8, we obtain a charge carrier density of 2.9 x 10(14)/cm2 at VG=2 V; this charge injection density corresponds to the conversion of slightly more than one monolayer of PTCDI-C8 molecules into anions. At higher gate bias voltage, electrochemical doping involving the intercalation of Li+ into the organic semiconductor film can convert all PTCDI-C8 molecules in a 30-nm film into anionic species. For comparison, when a conventional gate dielectric (polystyrene) is used, the maximum charge carrier density achievable at VG=200 V is approximately 4.5 x 10(13)/cm2, which corresponds to the conversion of 18% of a monolayer of PTCDI-C8 molecules into anions.

Polymer Electrolyte-Gated Organic Field-Effect Transistors: Low-Voltage, High-Current Switches for Organic Electronics and Testbeds for Probing Electrical Transport at High Charge Carrier Density

We report the fabrication and extensive characterization of solid polymer electrolyte-gated organic field-effect transistors (PEG-FETs) in which a polyethylene oxide (PEO) film containing a dissolved Li salt is used to modulate the hole conductivity of a polymer semiconductor. The large capacitance (approximately 10 microF/cm2) of the solution-processed polymer electrolyte gate dielectric facilitates polymer semiconductor conductivities on the order of 103 S/cm at low gate voltages (<3 V). In PEG-FETs based on regioregular poly(3-hexylthiophene), gate-induced hole densities were 2 x 10(14) charges/cm2 with mobilities >3 cm2/V.s. PEG-FETs fabricated with gate electrodes either aligned or intentionally nonaligned to the channel exhibited dramatically different electrical behavior when tested in vacuum or in air. Large differences in ionic diffusivity can explain the dominance of either electrostatic charging (in vacuum) or bulk electrochemical doping (in air) as the device operational mechanism. The use of a larger anion in the polymer electrolyte, bis(trifluoromethanesulfonyl)imide (TFSI-), yielded transistors that showed clear current saturation and square law behavior in the output characteristics, which also points to electrostatic (field-effect) charging. In addition, negative transconductances were observed using the PEO/LiTFSI electrolyte for all three polymer semiconductors at gate voltages larger than -3 V. Bias stress measurements performed with PEO/LiTFSI-gated bottom contact PEG-FETs showed that polymer semiconductors can sustain high ON currents for greater than 10 min without large losses in conductance. Collectively, the results indicate that PEG-FETs may serve as useful devices for high-current/low-voltage applications and as testbeds for probing electrical transport in polymer semiconductors at high charge density.

High charge carrier densities and conductance maxima in single-crystal organic field-effect transistors with a polymer electrolyte gate dielectric

High charge carrier densities have been realized in organic field-effect transistors based on single crystals of the organic semiconductors rubrene and tetracene using a high capacitance polymer electrolyte gate dielectric. The source-drain current was modulated by five orders of magnitude in a rubrene single-crystal organic field-effect transistor (SC-OFET) with gate voltages ranging from 0to−3V. A peak in the field-effect conductance was also observed in SC-OFETs at induced carrier densities of ∼1015charges∕cm2. Key to successful device fabrication was the introduction of a thin, insulating spacer layer between the organic single crystal (OSC) and the polymer electrolyte gate dielectric. Further improvement of the device fabrication procedure may eliminate suspected solvent-related degradation effects and raise mobility values in these SC-OFETs, opening the door to a wide spectrum of experiments on OSCs at high charge carrier densities.

Polymer Electrolyte Gating of Carbon Nanotube Network Transistors

Network behavior in single-walled carbon nanotubes (SWNTs) is examined by polymer electrolyte gating. High gate efficiencies, low voltage operation, and the absence of hysteresis in polymer electrolyte gating lead to a convenient and effective method of analyzing transport in SWNT networks. Furthermore, the ability to control carrier type with chemical groups of the host polymer allows us to examine both electron and hole conduction. Comparison to back gate measurements is made on channel length scaling. Frequency measurements are also made giving an upper limit of approximately 300 Hz switching speed for poly(ethylene oxide)/LiClO(4) gated SWNT thin film transistors.

Polymer Electrolyte Gate Dielectric Reveals Finite Windows of High Conductivity in Organic Thin Film Transistors at High Charge Carrier Densities

Finite regions of high conductivity were observed in both n- and p-channel organic thin film transistors based on polycrystalline organic semiconductor films and a solution-processed, solid polymer electrolyte gate dielectric. The transition from a highly conductive state to a more insulating state with increasing gate bias may be attributed to the realization of carrier densities greater than 1014 charges/cm2 in the semiconductor film.

Low-voltage operation of a pentacene field-effect transistor with a polymer electrolyte gate dielectric

Large operating voltages are often required to switch organic field-effect transistors (OFETs) on and off because commonly used gate dielectric layers provide low capacitive coupling between the gate electrode and the semiconductor. We present here a pentacene OFET gated by a solution-deposited polymer electrolyte film in which the current was modulated over four orders of magnitude using gate voltages less than 2V. A subthreshold slope of 180mV per decade of current was observed during transistor turn on at a source-drain bias of −1V; the estimated dielectric layer specific capacitance was 5μF∕cm2. Sweep rate-dependent hysteresis may be attributed to a combination of ion migration and charge carrier trapping effects. Strategies to improve switching speeds for polymer electrolyte-gated OFETs are also discussed.