Michael L. Geier

Inkjet Printing of High Conductivity, Flexible Graphene Patterns

The ability to print high conductivity, conformal, and flexible electrodes is an important technological challenge in printed electronics, especially for large-area formats with low cost considerations. In this Letter, we demonstrate inkjet-printed, high conductivity graphene patterns that are suitable for flexible electronics. The ink is prepared by solution-phase exfoliation of graphene using an environmentally benign solvent, ethanol, and a stabilizing polymer, ethyl cellulose. The inkjet-printed graphene features attain low resistivity of 4 mΩ·cm after a thermal anneal at 250 °C for 30 min while showing uniform morphology, compatibility with flexible substrates, and excellent tolerance to bending stresses.

Gate-tunable carbon nanotube–MoS2 heterojunction p-n diode

Significance The p-n junction diode is the most ubiquitous and fundamental building block of modern electronics, with far-reaching applications including integrated circuits, detectors, photovoltaics, and lasers. With the recent discovery and study of atomically thin materials, opportunities exist for adding new functionality to the p-n junction diode. Here we demonstrate that a p-n heterojunction diode based on atomically thin MoS2 and sorted semiconducting carbon nanotubes yields unprecedented gate tunability in both its electrical and optical properties, which is not observed in the case of bulk semiconductor devices. In addition to enabling advanced electronic and optoelectronic technologies, this p-n heterojunction diode provides new insight into charge transport and separation at atomically thin heterointerfaces. The p-n junction diode and field-effect transistor are the two most ubiquitous building blocks of modern electronics and optoelectronics. In recent years, the emergence of reduced dimensionality materials has suggested that these components can be scaled down to atomic thicknesses. Although high-performance field-effect devices have been achieved from monolayered materials and their heterostructures, a p-n heterojunction diode derived from ultrathin materials is notably absent and constrains the fabrication of complex electronic and optoelectronic circuits. Here we demonstrate a gate-tunable p-n heterojunction diode using semiconducting single-walled carbon nanotubes (SWCNTs) and single-layer molybdenum disulfide as p-type and n-type semiconductors, respectively. The vertical stacking of these two direct band gap semiconductors forms a heterojunction with electrical characteristics that can be tuned with an applied gate bias to achieve a wide range of charge transport behavior ranging from insulating to rectifying with forward-to-reverse bias current ratios exceeding 104. This heterojunction diode also responds strongly to optical irradiation with an external quantum efficiency of 25% and fast photoresponse <15 μs. Because SWCNTs have a diverse range of electrical properties as a function of chirality and an increasing number of atomically thin 2D nanomaterials are being isolated, the gate-tunable p-n heterojunction concept presented here should be widely generalizable to realize diverse ultrathin, high-performance electronics and optoelectronics.

Aerosol jet printed, low voltage, electrolyte gated carbon nanotube ring oscillators with sub-5 μs stage delays.

A central challenge for printed electronics is to achieve high operating frequencies (short transistor switching times) at low supply biases compatible with thin film batteries. In this report, we demonstrate partially printed five-stage ring oscillators with >20 kHz operating frequencies and stage delays <5 μs at supply voltages below 3 V. The fastest ring oscillator achieved 1.2 μs delay time at 2 V supply. The inverter stages in these ring oscillators were based on ambipolar thin film transistors (TFTs) employing semiconducting, single-walled carbon nanotube (CNT) networks and a high capacitance (∼1 μF/cm(2)) ion gel electrolyte as the gate dielectric. All materials except the source and drain electrodes were aerosol jet printed. The TFTs exhibited high electron and hole mobilities (∼20 cm(2)/(V s)) and ON/OFF current ratios (up to 10(5)). Inverter switching times t were systematically characterized as a function of transistor channel length and ionic conductivity of the gel dielectric, demonstrating that both the semiconductor and the ion gel play a role in switching speed. Quantitative scaling analysis suggests that with suitable optimization low voltage, printed ion gel gated CNT inverters could operate at frequencies on the order of 1 MHz.

Solution-processed carbon nanotube thin-film complementary static random access memory.

Over the past two decades, extensive research on single-walled carbon nanotubes (SWCNTs) has elucidated their many extraordinary properties, making them one of the most promising candidates for solution-processable, high-performance integrated circuits. In particular, advances in the enrichment of high-purity semiconducting SWCNTs have enabled recent circuit demonstrations including synchronous digital logic, flexible electronics and high-frequency applications. However, due to the stringent requirements of the transistors used in complementary metal-oxide-semiconductor (CMOS) logic as well as the absence of sufficiently stable and spatially homogeneous SWCNT thin-film transistors, the development of large-scale SWCNT CMOS integrated circuits has been limited in both complexity and functionality. Here, we demonstrate the stable and uniform electronic performance of complementary p-type and n-type SWCNT thin-film transistors by controlling adsorbed atmospheric dopants and incorporating robust encapsulation layers. Based on these complementary SWCNT thin-film transistors, we simulate, design and fabricate arrays of low-power static random access memory circuits, achieving large-scale integration for the first time based on solution-processed semiconductors.

High-Speed, Inkjet-Printed Carbon Nanotube/Zinc Tin Oxide Hybrid Complementary Ring Oscillators

The materials combination of inkjet-printed single-walled carbon nanotubes (SWCNTs) and zinc tin oxide (ZTO) is very promising for large-area thin-film electronics. We compare the characteristics of conventional complementary inverters and ring oscillators measured in air (with SWCNT p-channel field effect transistors (FETs) and ZTO n-channel FETs) with those of ambipolar inverters and ring oscillators comprised of bilayer SWCNT/ZTO FETs. This is the first such comparison between the performance characteristics of ambipolar and conventional inverters and ring oscillators. The measured signal delay per stage of 140 ns for complementary ring oscillators is the fastest for any ring oscillator circuit with printed semiconductors to date.

Subnanowatt Carbon Nanotube Complementary Logic Enabled by Threshold Voltage Control

In this Letter, we demonstrate thin-film single-walled carbon nanotube (SWCNT) complementary metal-oxide-semiconductor (CMOS) logic devices with subnanowatt static power consumption and full rail-to-rail voltage transfer characteristics as is required for logic gate cascading. These results are enabled by a local metal gate structure that achieves enhancement-mode p-type and n-type SWCNT thin-film transistors (TFTs) with widely separated and symmetric threshold voltages. These complementary SWCNT TFTs are integrated to demonstrate CMOS inverter, NAND, and NOR logic gates at supply voltages as low as 0.8 V with ideal rail-to-rail operation, subnanowatt static power consumption, high gain, and excellent noise immunity. This work provides a direct pathway for solution processable, large area, power efficient SWCNT advanced logic circuits and systems.

Ambient-Processable High Capacitance Hafnia-Organic Self- Assembled Nanodielectrics

Ambient and solution-processable, low-leakage, high capacitance gate dielectrics are of great interest for advances in low-cost, flexible, thin-film transistor circuitry. Here we report a new hafnium oxide-organic self-assembled nanodielectric (Hf-SAND) material consisting of regular, alternating π-electron layers of 4-[[4-[bis(2-hydroxyethyl)amino]phenyl]diazenyl]-1-[4-(diethoxyphosphoryl) benzyl]pyridinium bromide) (PAE) and HfO2 nanolayers. These Hf-SAND multilayers are grown from solution in ambient with processing temperatures ≤150 °C and are characterized by AFM, XPS, X-ray reflectivity (2.3 nm repeat spacing), X-ray fluorescence, cross-sectional TEM, and capacitance measurements. The latter yield the largest capacitance to date (1.1 μF/cm(2)) for a solid-state solution-processed hybrid inorganic-organic gate dielectric, with effective oxide thickness values as low as 3.1 nm and have gate leakage <10(-7) A/cm(2) at ±2 MV/cm using photolithographically patterned contacts (0.04 mm(2)). The sizable Hf-SAND capacitances are attributed to relatively large PAE coverages on the HfO2 layers, confirmed by X-ray reflectivity and X-ray fluorescence. Random network semiconductor-enriched single-walled carbon nanotube transistors were used to test Hf-SAND utility in electronics and afforded record on-state transconductances (5.5 mS) at large on:off current ratios (I(ON):I(OFF)) of ~10(5) with steep 150 mV/dec subthreshold swings and intrinsic field-effect mobilities up to 137 cm(2)/(V s). Large-area devices (>0.2 mm(2)) on Hf-SAND (6.5 nm thick) achieve mA on currents at ultralow gate voltages (<1 V) with low gate leakage (<2 nA), highlighting the defect-free and conformal nature of this nanodielectric. High-temperature annealing in ambient (400 °C) has limited impact on Hf-SAND leakage densities (<10(-6) A/cm(2) at ±2 V) and enhances Hf-SAND multilayer capacitance densities to nearly 1 μF/cm(2), demonstrating excellent compatibility with device postprocessing methodologies. These results represent a significant advance in hybrid organic-inorganic dielectric materials and suggest synthetic routes to even higher capacitance materials useful for unconventional electronics.

Low voltage, high performance inkjet printed carbon nanotube transistors with solution processed ZrO2 gate insulator

High-performance single-walled carbon nanotube (SWCNT) thin-film transistors are fabricated by single-pass inkjet printing of SWCNTs on high-κ solution-processed ZrO2 gate dielectric. We demonstrate that an ultraviolet ozone treatment of the ZrO2 substrate is critical in achieving a uniform dispersion of sorted SWCNTs in the semiconducting channel. The resulting devices exhibit excellent performance with mobility and on/off current ratio exceeding 30 cm2 V−1 s−1 and 105, respectively, at low operating voltages (<5 V). The single-pass inkjet printing process demonstrated in this letter shows great promise as a reliable and scalable method for SWCNT based high performance electronics.

Utilizing carbon nanotube electrodes to improve charge injection and transport in bis(trifluoromethyl)-dimethyl-rubrene ambipolar single crystal transistors

We have examined the significant enhancement of ambipolar charge injection and transport properties of bottom-contact single crystal field-effect transistors (SC-FETs) based on a new rubrene derivative, bis(trifluoromethyl)-dimethyl-rubrene (fm-rubrene), by employing carbon nanotube (CNT) electrodes. The fundamental challenge associated with fm-rubrene crystals is their deep-lying HOMO and LUMO energy levels, resulting in inefficient hole injection and suboptimal electron injection from conventional Au electrodes due to large Schottky barriers. Applying thin layers of CNT network at the charge injection interface of fm-rubrene crystals substantially reduces the contact resistance for both holes and electrons; consequently, benchmark ambipolar mobilities have been achieved, reaching 4.8 cm(2) V(-1) s(-1) for hole transport and 4.2 cm(2) V(-1) s(-1) for electron transport. We find that such improved injection efficiency in fm-rubrene is beneficial for ultimately unveiling its intrinsic charge transport properties so as to exceed those of its parent molecule, rubrene, in the current device architecture. Our studies suggest that CNT electrodes may provide a universal approach to ameliorate the charge injection obstacles in organic electronic devices regardless of charge carrier type, likely due to the electric field enhancement along the nanotube located at the crystal/electrode interface.

Fluoropolymer coatings for improved carbon nanotube transistor device and circuit performance

We report on the marked improvements in key device characteristics of single walled carbon nanotube (SWCNT) field-effect transistors (FETs) by coating the active semiconductor with a fluoropolymer layer such as poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE). The observed improvements include: (i) A reduction in off-current by about an order of magnitude, (ii) a significant reduction in the variation of threshold voltage, and (iii) a reduction in bias stress-related instability and hysteresis present in device characteristics. These favorable changes in device characteristics also enhance circuit performance and the oscillation amplitude, oscillation frequency, and increase the yield of printed complementary 5-stage ring oscillators. The origins of these improvements are explored by exposing SWCNT FETs to a number of vapor phase polar molecules which produce similar effects on the FET characteristics as the PVDF-TrFE. Coating of the active SWCNT semiconductor layer with a fluoropolymer will be adv...