A hybrid transistor with transcriptionally controlled computation and plasticity.

Organic electrochemical transistors (OECTs) are ideal devices for translating biological signals into electrical readouts and have applications in bioelectronics, biosensing, and neuromorphic computing. Despite their potential, developing programmable and modular methods for living systems to interface with OECTs has proven challenging. Here we describe hybrid OECTs containing the model electroactive bacterium Shewanella oneidensis that enable the transduction of biological computations to electrical responses. Specifically, we fabricated planar p-type OECTs and demonstrated that channel de-doping is driven by extracellular electron transfer (EET) from S. oneidensis. Leveraging this mechanistic understanding and our ability to control EET flux via transcriptional regulation, we used plasmid-based Boolean logic gates to translate biological computation into current changes within the OECT. Finally, we demonstrated EET-driven changes to OECT synaptic plasticity. This work enables fundamental EET studies and OECT-based biosensing and biocomputing systems with genetically controllable and modular design elements.

Visualization of Mesoscopic Conductivity Fluctuations in Amorphous Semiconductor Thin-Film Transistors.

Charge transport in amorphous semiconductors is considerably more complicated than the process in crystalline materials due to abundant localized states. In addition to device-scale characterization, spatially resolved measurements are important to unveiling electronic properties. Here, we report gigahertz conductivity mapping in amorphous indium gallium zinc oxide (a-IGZO) thin-film transistors by microwave impedance microscopy (MIM), which probes conductivity without Schottky barrier's influence. The difference between the dc and microwave conductivities reflects the efficacy of the injection barrier in an accumulation-mode transistor. The conductivity exhibits significant nanoscale inhomogeneity in the subthreshold regime, presumably due to trapping and release from localized states. The characteristic length scale of local fluctuations, as determined by the autocorrelation analysis, is about 200 nm. Using a random-barrier model, we can simulate the spatial variation of the potential landscape, which underlies the mesoscopic conductivity distribution. Our work provides an intuitive way to understand the charge transport mechanism in amorphous semiconductors at the microscopic level.

A Hybrid Transistor with Transcriptionally Controlled Computation and Plasticity.

Organic electrochemical transistors (OECTs) are ideal devices for translating biological signals into electrical readouts and have applications in bioelectronics, biosensing, and neuromorphic computing. Despite their potential, developing programmable and modular methods for living systems to interface with OECTs has proven challenging. Here we describe hybrid OECTs containing the model electroactive bacterium Shewanella oneidensis that enable the transduction of biological computations to electrical responses. Specifically, we fabricated planar p-type OECTs and demonstrated that channel de-doping is driven by extracellular electron transfer (EET) from S. oneidensis. Leveraging this mechanistic understanding and our ability to control EET flux via transcriptional regulation, we used plasmid-based Boolean logic gates to translate biological computation into current changes within the OECT. Finally, we demonstrated EET-driven changes to OECT synaptic plasticity. This work enables fundamental EET studies and OECT-based biosensing and biocomputing systems with genetically controllable and modular design elements.

Wafer-Scalable Single-Layer Amorphous Molybdenum Trioxide.

Molybdenum trioxide (MoO3), an important transition metal oxide (TMO), has been extensively investigated over the past few decades due to its potential in existing and emerging technologies, including catalysis, energy and data storage, electrochromic devices, and sensors. Recently, the growing interest in two-dimensional (2D) materials, often rich in interesting properties and functionalities compared to their bulk counterparts, has led to the investigation of 2D MoO3. However, the realization of large-area true 2D (single to few atom layers thick) MoO3 is yet to be achieved. Here, we demonstrate a facile route to obtain wafer-scale monolayer amorphous MoO3 using 2D MoS2 as a starting material, followed by UV-ozone oxidation at a substrate temperature as low as 120 °C. This simple yet effective process yields smooth, continuous, uniform, and stable monolayer oxide with wafer-scale homogeneity, as confirmed by several characterization techniques, including atomic force microscopy, numerous spectroscopy methods, and scanning transmission electron microscopy. Furthermore, using the subnanometer MoO3 as the active layer sandwiched between two metal electrodes, we demonstrate the thinnest oxide-based nonvolatile resistive switching memory with a low voltage operation and a high ON/OFF ratio. These results (potentially extendable to other TMOs) will enable further exploration of subnanometer stoichiometric MoO3, extending the frontiers of ultrathin flexible oxide materials and devices.

Nanospike electrodes and charge nanoribbons: A new design for nanoscale thin-film transistors.

To scale down thin-film transistor (TFT) channel lengths for accessing higher levels of speed and performance, a redesign of the basic device structure is necessary. With nanospike-shaped electrodes, field-emission effects can be used to assist charge injection from the electrodes in sub-200-nm channel length amorphous oxide and organic TFTs. These designs result in the formation of charge nanoribbons at low gate biases that greatly improve subthreshold and turn-off characteristics. A design paradigm in which the gate electric field can be less than the source-drain field is proposed and demonstrated. By combining small channel lengths and thick gate dielectrics, this approach is also shown to be a promising solution for boosting TFT performance through charge focusing and charge nanoribbon formation in flexible/printed electronics applications.

Double-Gate MoS2 Field-Effect Transistor with a Multilayer Graphene Floating Gate: A Versatile Device for Logic, Memory, and Synaptic Applications.

2D materials with low-temperature processing hold promise for electronic devices that augment conventional silicon technology. To meet this promise, devices should have capabilities not easily achieved with silicon technology, including planar fully-depleted silicon-on-insulator with substrate body-bias, or vertical finFETs with no body-bias capability. In this work, we fabricate and characterize a device [a double-gate MoS2 field-effect transistor (FET) with hexagonal boron nitride (h-BN) gate dielectrics and a multi-layer graphene floating gate (FG)] in multiple operating conditions to demonstrate logic, memory, and synaptic applications; a range of h-BN thicknesses is investigated for charge retention in the FG. In particular, we demonstrate this device as a (i) logic FET with adjustable VT by charges stored in the FG, (ii) digital flash memory with lower pass-through voltage to enable improved reliability, and (iii) synaptic device with decoupling of tunneling and gate dielectrics to achieve a symmetric program/erase conductance change. Overall, this versatile device, compatible to back-end-of-line integration, could readily augment silicon technology.

Enhanced Photoresponse in Metasurface-Integrated Organic Photodetectors.

In this work, we experimentally demonstrate metasurface-enhanced photoresponse in organic photodetectors. We have designed and integrated a metasurface with broadband functionality into an organic photodetector, with the goal of significantly increasing the absorption of light and generated photocurrent from 560 up to 690 nm. We discuss how the metasurface can be integrated with the fabrication of an organic photodiode. Our results show large gains in responsivity from 1.5× to 2× between 560 and 690 nm.

Inkjet printed circuits based on ambipolar and p-type carbon nanotube thin-film transistors.

Ambipolar and p-type single-walled carbon nanotube (SWCNT) thin-film transistors (TFTs) are reliably integrated into various complementary-like circuits on the same substrate by inkjet printing. We describe the fabrication and characteristics of inverters, ring oscillators, and NAND gates based on complementary-like circuits fabricated with such TFTs as building blocks. We also show that complementary-like circuits have potential use as chemical sensors in ambient conditions since changes to the TFT characteristics of the p-channel TFTs in the circuit alter the overall operating characteristics of the circuit. The use of circuits rather than individual devices as sensors integrates sensing and signal processing functions, thereby simplifying overall system design.

Inkjet-Printed Lithium-Sulfur Microcathodes for All-Printed, Integrated Nanomanufacturing.

Improved thin-film microbatteries are needed to provide appropriate energy-storage options to power the multitude of devices that will bring the proposed "Internet of Things" network to fruition (e.g., active radio-frequency identification tags and microcontrollers for wearable and implantable devices). Although impressive efforts have been made to improve the energy density of 3D microbatteries, they have all used low energy-density lithium-ion chemistries, which present a fundamental barrier to miniaturization. In addition, they require complicated microfabrication processes that hinder cost-competitiveness. Here, inkjet-printed lithium-sulfur (Li-S) cathodes for integrated nanomanufacturing are reported. Single-wall carbon nanotubes infused with electronically conductive straight-chain sulfur (S@SWNT) are adopted as an integrated current-collector/active-material composite, and inkjet printing as a top-down approach to achieve thin-film shape control over printed electrode dimensions is used. The novel Li-S cathodes may be directly printed on traditional microelectronic semicoductor substrates (e.g., SiO2 ) or on flexible aluminum foil. Profilometry indicates that these microelectrodes are less than 10 µm thick, while cyclic voltammetry analyses show that the S@SWNT possesses pseudocapacitive characteristics and corroborates a previous study suggesting the S@SWNT discharge via a purely solid-state mechanism. The printed electrodes produce ≈800 mAh g-1 S initially and ≈700 mAh g-1 after 100 charge/discharge cycles at C/2 rate.

Long-Term Stability and Reliability of Black Phosphorus Field-Effect Transistors.

Black phosphorus has been recently suggested as a very promising material for use in 2D field-effect transistors. However, due to its poor stability under ambient conditions, this material has not yet received as much attention as for instance MoS2. We show that the recently demonstrated Al2O3 encapsulation leads to highly stable devices. In particular, we report our long-term study on highly stable black phosphorus field-effect transistors, which show stable device characteristics for at least eight months. This high stability allows us to perform a detailed analysis of their reliability with respect to hysteresis as well as the arguably most important reliability issue in silicon technologies, the bias-temperature instability. We find that the hysteresis in these transistors depends strongly on the sweep rate and temperature. Moreover, the hysteresis dynamics in our devices are reproducible over a long time, which underlines their high reliability. Also, by using detailed physical models for oxide traps developed for Si technologies, we are able to capture the channel electrostatics of the black phosphorus FETs and determine the position of the defect energy band. Finally, we demonstrate that both hysteresis and bias-temperature instabilities are due to thermally activated charge trapping/detrapping by oxide traps and can be reduced if the device is covered by Teflon-AF.

Inkjet Printed Circuits on Flexible and Rigid Substrates Based on Ambipolar Carbon Nanotubes with High Operational Stability.

Inkjet printed ambipolar transistors and circuits with high operational stability are demonstrated on flexible and rigid substrates employing semiconducting single-walled carbon nanotubes (SWCNTs). All patterns, which include electrodes, semiconductors, and vias, are realized by inkjet printing without the use of rigid physical masks and photolithography. An Al2O3 layer deposited on devices by atomic layer deposition (ALD) transforms p-type SWCNT thin-film transistors (TFTs) into ambipolar SWCNT TFTs and encapsulates them effectively. The ambipolar SWCNT TFTs have balanced electron and hole mobilities, which facilitates their use in multicomponent circuits. For example, a variety of logic gates and ring oscillators are demonstrated based on the ambipolar TFTs. The three-stage ring oscillator operates continuously for longer than 80 h under ambient conditions with only slight deviations in oscillation frequency. The successful demonstration of ambipolar devices by inkjet printing will enable a new class of circuits that utilize n-channel, p-channel, and ambipolar circuit components.

Short Channel Field-Effect-Transistors with Inkjet-Printed Semiconducting Carbon Nanotubes.

Short channel field-effect-transistors with inkjet-printed semiconducting carbon nanotubes are fabricated using a novel strategy to minimize material consumption, confining the inkjet droplet into the active channel area. This fabrication approach is compatible with roll-to-roll processing and enables the formation of high-performance short channel device arrays based on inkjet printing.

Dramatic vapor-phase modulation of the characteristics of graphene field-effect transistors.

Here we report on dramatic and favorable changes to the operating characteristics in monolayer graphene field-effect transistors (FETs) exposed to vapor-phase, polar organic molecules in ambient. These changes include significant reduction of the Dirac voltage, accompanied by both an increase in electron and hole mobility, µ, and a decrease in residual carrier density, N0, to < 3 × 10(11) cm(-2). In contrast to graphene FET modulation with various liquid- and solid-phase dielectric media present in the literature, we attribute these changes to screening by polar vapor-phase molecules of fields induced by charged impurities and defects, n(imp), in or near the active layer. The magnitude of the changes produced in the graphene FET parameters scales remarkably well with the dipole moment of the delivered molecules. These effects are reversible, a unique advantage of working in the vapor phase. The changes observed upon polar molecule delivery are analogous to those produced by depositing and annealing fluoropolymer coatings on graphene that have been reported previously, and we attribute these changes to similar charge screening or neutralization phenomena.

Efficient polymer solar cells enabled by low temperature processed ternary metal oxide as electron transport interlayer with large stoichiometry window.

Highly efficient organic photovoltaic cells are demonstrated by incorporating low temperature solution processed indium zinc oxide (IZO) as cathode interlayers. The IZOs are synthesized using a combustion synthesis method, which enables low temperature processes (150-250 °C). We investigated the IZO films with different electron mobilities (1.4×10(-3) to 0.23 cm2/(V·s)), hydroxide-oxide content (38% to 47%), and surface roughness (0.19-5.16 nm) by modulating the ternary metal oxide stoichiometry. The photovoltaic performance was found to be relatively insensitive to the composition ratio of In:Zn over the range of 0.8:0.2 to 0.5:0.5 despite the differences in their electrical and surface properties, achieving high power conversion efficiencies of 6.61%-7.04%. Changes in composition ratio of IZO do not lead to obvious differences in energy levels, diode parameters and morphology of the photoactive layer, as revealed by ultraviolet photoelectron spectroscopy (UPS), dark current analysis and time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurements, correlating well with the large IZO stoichiometry window that enables efficient photovoltaic devices. Our results demonstrate the robustness of this ETL system and provide a convenient approach to realize a wide range of multicomponent oxides and compatible with processing on flexible plastic substrates.

Voltage-Controlled Ring Oscillators Based on Inkjet Printed Carbon Nanotubes and Zinc Tin Oxide.

A voltage-controlled ring oscillator is implemented with double-gate complementary transistors where both the n- and p-channel semiconductors are deposited by inkjet printing. Top gates added to transistors in conventional ring oscillator circuits control not only threshold voltages of the constituent transistors but also the oscillation frequencies of the ring oscillators. The oscillation frequency increases or decreases linearly with applied top gate potential. The field-effect transistor materials system that yields such linear behavior has not been previously reported. In this work, we demonstrate details of a material system (gate insulator, p- and n-channel semiconductors) that results in very linear frequency changes with control gate potential. Our use of a double layer top dielectric consisting of a combination of solution processed P(VDF-TrFE) and Al2O3 deposited by atomic layer deposition leads to low operating voltages and near-optimal device characteristics from a circuit standpoint. Such functional blocks will enable the realization of printed voltage-controlled oscillator-based analog-to-digital converters.

Toward air-stable multilayer phosphorene thin-films and transistors.

Few-layer black phosphorus (BP), also known as phosphorene, is poised to be the most attractive graphene analogue owing to its high mobility approaching that of graphene, and its thickness-tunable band gap that can be as large as that of molybdenum disulfide. In essence, phosphorene represents the much sought after high-mobility, large direct band gap two-dimensional layered crystal that is ideal for optoelectronics and flexible devices. However, its instability in air is of paramount concern for practical applications. Here, we demonstrate air-stable BP devices with dielectric and hydrophobic encapsulation. Microscopy, spectroscopy, and transport techniques were employed to elucidate the aging mechanism, which can initiate from the BP surface for bare samples, or edges for samples with thin dielectric coating, highlighting the ineffectiveness of conventional scaled dielectrics. Our months-long studies indicate that a double layer capping of Al2O3 and hydrophobic fluoropolymer affords BP devices and transistors with indefinite air-stability for the first time, overcoming a critical material challenge for applied research and development.

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.

Improved performance in diketopyrrolopyrrole-based transistors with bilayer gate dielectrics.

There has been significant progress in the past 2 decades in the field of organic and polymer thin-film transistors. In this paper, we report a combination of stable materials, device architecture, and process conditions that resulted in a patterned gate, small channel length (<5 µm) device that possesses a scaled field-induced conductivity in air that is higher than any organic/polymer transistor reported thus far. The operating voltage is below 10 V; the on-off ratio is high; and the active materials are solution-processable. The semiconducting polymer is a new donor-acceptor polymer with furan-substituted diketopyrrolopyrrole and thienyl-vinylene-thienyl building blocks in the conjugated backbone. One of the major striking features of our work is that the patterned-gate device architecture is suitable for practical applications. We also propose a figure of merit to meaningfully compare polymer/organic transistor performance that takes into account mobility and operating voltage. With this figure of merit, we compare leading organic and polymer transistors that have been hitherto reported. The material and device architecture have shown very high mobility and low operating voltage for such short channel length (below 5 µm) organic/polymer transistors.

Water-based nanoparticulate solar cells using a diketopyrrolopyrrole donor polymer.

Organic photovoltaic devices with either bulk heterojunction (BHJ) or nanoparticulate (NP) active layers have been prepared from a 1 : 2 blend of (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene}) (PDPP-TNT) and the fullerene acceptor, ([6,6]-phenyl C71-butyric acid methyl ester) (PC70BM). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) have been used to investigate the morphology of the active layers of the two approaches. Mild thermal treatment of the NP film is required to promote initial joining of the NPs in order for the devices to function, however the NP structure is retained. Consequently, whereas gross phase segregation of the active layer occurs in the BHJ device spin cast from chloroform, the nanoparticulate approach retains control of the material domain sizes on the length scale of exciton diffusion in the materials. As a result, NP devices are found to generate more than twice the current density of BHJ devices and have a substantially greater overall efficiency. The use of aqueous nanoparticulate dispersions offers a promising approach to control the donor acceptor morphology on the nanoscale with the benefit of environmentally-friendly, solution-based fabrication.

Synthesis of diketopyrrolopyrrole based copolymers via the direct arylation method for p-channel and ambipolar OFETs.

In this paper, we have synthesized two novel diketopyrrolopyrrole (DPP) based donor­acceptor (D­A) copolymers poly{3,6-dithiophene-2-yl-2,5-di(2-octyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-1,5-bis(dodecyloxy)naphthalene} (PDPPT-NAP) and poly{3,6-dithiophene-2-yl-2,5-di(2-butyldecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-2-dodecyl-2H-benzo[d][1,2,3]triazole} (PDPPT-BTRZ) via direct arylation organometallic coupling. Both copolymers contain a common electron withdrawing DPP building block which is combined with electron donating alkoxy naphthalene and electron withdrawing alkyl-triazole comonomers. The number average molecular weight (M(n)) determined by gel permeation chromatography (GPC) for polymer PDPPT-NAP is around 23400 g mol(−1) whereas for polymer PDPPT-BTRZ it is 18600 g mol(−1). The solid state absorption spectra of these copolymers show a wide range of absorption from 400 nm to 1000 nm with optical band gaps calculated from absorption cut off values in the range of 1.45­1.30 eV. The HOMO values determined for PDPPT-NAP and PDPPT-BTRZ copolymers from photoelectron spectroscopy in air (PESA) data are 5.15 eV and 5.25 eV respectively. These polymers exhibit promising p-channel and ambipolar behaviour when used as an active layer in organic thin-film transistor (OTFT) devices. The highest hole mobility measured for polymer PDPPT-NAP is around 0.0046 cm(2) V(−1) s(−1) whereas the best ambipolar performance was calculated for PDPPT-BTRZ with a hole and electron mobility of 0.01 cm(2) V(−1) s(−1) and 0.006 cm(2) V(−1) s(−1) .