Graphene Solution‐Gated Field‐Effect Transistor Array for Sensing Applications

Graphene, with its unique combination of physical and electronic properties, holds great promise for biosensor and bioelectronic applications. In this respect, the development of graphene solution‐gated field‐effect transistor (SGFET) arrays capable of operation in aqueous environments will establish the real potential of graphene in this rapidly emerging field. Here, we report on a facile route for the scalable fabrication of such graphene transistor arrays and provide a comprehensive characterization of their operation in aqueous electrolytes. An on‐chip structure for Hall‐effect measurements allows the direct determination of charge carrier concentrations and mobilities under electrolyte gate control. The effect of the solution‐gate potential on the electronic properties of graphene is explained using a model that considers the microscopic structure of water at the graphene/electrolyte interface. The graphene SGFETs exhibit a high transconductance and correspondingly high sensitivity, together with an effective gate noise as low as tens of μV. Our study demonstrates that graphene SGFETs, with their facile technology, high transconductance, and low noise promise to far outperform state‐of‐the‐art Si‐based devices for biosensor and bioelectronic applications.     

Large‐Area Schottky Barrier Transistors Based on Vertically Stacked Graphene–Metal Oxide Heterostructures

The fabrication of all‐transparent flexible vertical Schottky barrier (SB) transistors and logic gates based on graphene–metal oxide–metal heterostructures and ion gel gate dielectrics is demonstrated. The vertical SB transistor structure is formed by (i) vertically sandwiching a solution‐processed indium‐gallium‐zinc‐oxide (IGZO) semiconductor layer between graphene (source) and metallic (drain) electrodes and (ii) employing a separate coplanar gate electrode bridged with a vertical channel through an ion gel. The channel current is modulated by tuning the Schottky barrier height across the graphene–IGZO junction under an applied external gate bias. The ion gel gate dielectric with high specific capacitance enables modulation of the Schottky barrier height at the graphene–IGZO junction over 0.87 eV using a voltage below 2 V. The resulting vertical devices show high current densities (18.9 A cm^?2) and on–off current ratios (>10⁴) at low voltages. The simple structure of the unit transistor enables the successful fabrication of low‐power logic gates based on device assemblies, such as the NOT, NAND, and NOR gates, prepared on a flexible substrate. The facile, large‐area, and room‐temperature deposition of both semiconducting metal oxide and gate insulators integrates with transparent and flexible graphene opens up new opportunities for realizing graphene‐based future electronics.     

Effect of Gate Electrode Work‐Function on Source Charge Injection in Electrolyte‐Gated Organic Field‐Effect Transistors

Systematic investigation of the contact resistance in electrolyte‐gated organic field‐effect transistors (OFETs) demonstrates a dependence of source charge injection versus gate electrode work function. This analysis reveals contact‐limitations at the source metal‐semiconductor interface and shows that the contact resistance increases as low work function metals are used as the gate electrode. These findings are attributed to the establishment of a built‐in potential that is high enough to prevent the Fermi‐level pinning at the metal‐organic interface. This results in an unfavorable energetic alignment of the source electrode with the valence band of the organic semiconductor. Since the operating voltage in the electrolyte‐gated devices is on the same order as the variation of the work functions, it is possible to tune the contact resistance over more than one order of magnitude by varying the gate metal.     

Polymer Dielectrics and Orthogonal Solvent Effects for High‐Performance Inkjet‐Printed Top‐Gated P‐Channel Polymer Field‐Effect Transistors

We investigated the effects of a gate dielectric and its solvent on the characteristics of top‐gated organic field‐effect transistors (OFETs). Despite the rough top surface of the inkjet‐printed active features, the charge transport in an OFET is still favorable, with no significant degradation in performance. Moreover, the characteristics of the OFETs showed a strong dependency on the gate dielectrics used and its orthogonal solvents. Poly(3‐hexylthiophene) OFETs with a poly(methyl methacrylate) dielectric showed typical p‐type OFET characteristics. The selection of gate dielectric and solvent is very important to achieve high‐performance organic electronic circuits.     

Electrolyte‐Gated Synaptic Transistor with Oxygen Ions

Artificial synaptic devices are the essential hardware of neuromorphic computing systems, which can simultaneously perform signal processing and information storage between two neighboring artificial neurons. Emerging electrolyte‐gated transistors have attracted much attention for efficient synaptic emulation by using an addition gate terminal. Here, an electrolyte‐gated synaptic device based on the SrCoO_x (SCO) films is proposed. It is demonstrated that the reversible modulation of SCO phase transforms the brownmillerite SrCoO_2.5 and perovskite SrCoO_3?δ , through controlling the insertion and extraction of oxygen ions with electrolyte gating. Nonvolatile multilevel conduction states can be realized in the SCO films following this route. The synaptic functions such as the long‐term potentiation and depression of synaptic weight, spike‐timing‐dependent plasticity, as well as spiking logic operations in the device are successfully mimicked. These results provide an alternative avenue for future neuromorphic devices via electrolyte‐gated transistors with oxygen ions.     

Systematic Doping Control of CVD Graphene Transistors with Functionalized Aromatic Self‐Assembled Monolayers

Recent reports have shown that self‐assembled monolayers (SAMs) can induce doping effects in graphene transistors. However, a lack of understanding persists surrounding the quantitative relationship between SAM molecular design and its effects on graphene. In order to facilitate the fabrication of next‐generation graphene‐based devices it is important to reliably and predictably control the properties of graphene without negatively impacting its intrinsic high performance. In this study, SAMs with varying dipole magnitudes/directions are utilized and these values are directly correlated to changes in performance seen in graphene transistors. It is found that, by knowing the z‐component of the SAM dipole, one can reliably predict the shift in graphene charge neutrality point after taking into account the influence of the metal electrodes (which also play a role in doping graphene). This relationship is verified through density functional theory and comprehensive device studies utilizing atomic force microscopy, X‐ray photoelectron spectroscopy, Raman spectroscopy, and electrical characterization of graphene transistors. It is shown that properties of graphene transistors can be predictably controlled with SAMs when considering the total doping environment. Additionally, it is found that methylthio‐terminated SAMs strongly interact with graphene allowing for a cleaner graphene transfer and enhanced charge mobility.     

Non‐Lithographic Fabrication of All‐2D α‐MoTe2 Dual Gate Transistors

As one of the emerging new transition‐metal dichalcogenides materials, molybdenum ditelluride (α‐MoTe₂) is attracting much attention due to its optical and electrical properties. This study fabricates all‐2D MoTe₂‐based field effect transistors (FETs) on glass, using thin hexagonal boron nitride and thin graphene in consideration of good dielectric/channel interface and source/drain contacts, respectively. Distinguished from previous works, in this study, all 2D FETs with α‐MoTe₂ nanoflakes are dual‐gated for driving higher current. Moreover, for the present 2D dual gate FET fabrications on glass, all thermal annealing and lithography processes are intentionally exempted for fully non‐lithographic method using only van der Waal's forces. The dual‐gate MoTe₂ FET displays quite a high hole and electron mobility over ≈20 cm² V^?1 s^?1 along with ON/OFF ratio of ≈10⁵ in maximum as an ambipolar FET and also demonstrates high drain current of a few tens‐to‐hundred μA at a low operation voltage. It appears promising enough to drive organic light emitting diode pixels and NOR logic functions on glass.     

Multibit Optoelectronic Memory in Top‐Floating‐Gated van der Waals Heterostructures

Nonvolatile memories based on van der Waals heterostructures have been proved to be promising candidates for next‐generation data storage devices. However, little attention has been focused on the structure with separated floating and control gates (the floating gates and control gates distribute at the different side of the channels), which were recently predicted to be capable of further improving device performance. Here, nonvolatile multibit optoelectronic memories are demonstrated using MoS₂, hexagonal boron nitride (h‐BN), and graphene in a top‐floating‐gated structure. With separated top graphene floating gate, the devices show a large memory window (≈95 V) via sweeping gate voltage from 80 to ?80 V, a high on/off ratio (≈10⁶) with an ultralow dark current (≈10^?14 A), as well as excellent retention characteristic (≈10⁴ s) and cyclic endurance. In addition, these devices can also be erased by a laser illumination with broadband spectrum after being electrically programmed. For the multilevel storage property, 7/6 stages controlled by different electrical operations, and 13/6/3 stages by different laser pulse illuminations are gained. The obtained results show a promising performance for nonvolatile optoelectronic memory using a top‐floating‐gated structure.     

Reusable Cellulose‐Based Hydrogel Sticker Film Applied as Gate Dielectric in Paper Electrolyte‐Gated Transistors

A new concept for reusable eco‐friendly hydrogel electrolytes based on cellulose is introduced. The reported electrolytes are designed and engineered through a simple, fast, low‐cost, and eco‐friendly dissolution method of microcrystalline cellulose at low temperature using an aqueous LiOH/urea solvent system. The cellulose solution is combined with carboxymethyl cellulose, followed by the regeneration and simultaneous ion incorporation. The produced free standing cellulose‐based electrolyte films exhibit interesting properties for application in flexible electrochemical devices, such as biosensors or electrolyte‐gated transistors (EGTs), because of their high specific capacitances (4–5 µF cm^?2), transparency, and flexibility. Indium–gallium–zinc‐oxide EGTs on glass with laminated cellulose‐based hydrogel electrolytes (CHEs) as the gate dielectric are produced presenting a low working voltage (<2 V), showing an on–off current ratio (I _on/off) of 10⁶, a subthreshold swing lower than 0.2 V dec^?1, and saturation mobility (μ_Sat) reaching 26 cm² V^?1 s^?1. The flexible CHE‐gated transistors on paper are also demonstrated, which operate at switching frequencies up to 100 Hz. Combining the flexibility of the EGTs on paper with the reusability of the developed CHEs is a breakthrough toward biodegradable advanced functional materials allied with disposable/recyclable and low‐cost electronic devices.     

Label‐Free Electrical Detection of DNA Hybridization on Graphene using Hall Effect Measurements: Revisiting the Sensing Mechanism

There is broad interest in using graphene or graphene oxide sheets as a transducer for label‐free and selective electrical detection of biomolecules such as DNA. However, it is still not well explored how the DNA molecules interact with and influence the properties of graphene during the detection. Here, Hall effect measurements based on the Van der Pauw method are used to perform single‐base sequence selective detection of DNA on graphene sheets, which are prepared by chemical vapor deposition. The sheet resistance increases and the mobility decreases with the addition of either complementary or one‐base mismatched DNA to the graphene device. The hole carrier concentration of the graphene devices increases significantly with the addition of complementary DNA but it is less affected by the one‐base mismatched DNA. It is concluded that the increase in hole carrier density, indicating p‐doping to graphene, is better correlated with the DNA hybridization compared to the commonly used parameters such as conductivity change. The different electrical observations of p‐doping from Hall effect measurements and n‐doping from electrolyte‐gated transistors can be explained by the characteristic morphology of partially hybridized DNA on graphene and the mismatch between DNA chain length and Debye length in electrolytes.     

Gate Capacitance‐Dependent Field‐Effect Mobility in Solution‐Processed Oxide Semiconductor Thin‐Film Transistors

Solution‐processed oxide semiconductors (OSs) used as channel layer have been presented as a solution to the demand for flexible, cheap, and transparent thin‐film transistors (TFTs). In order to produce high‐performance and long‐sustainable portable devices with the solution‐processed OS TFTs, the low‐operational voltage driving current is a key issue. Experimentally, increasing the gate‐insulator capacitances by high‐k dielectrics in the OS TFTs has significantly improved the field‐effect mobility of the OS TFTs. But, methodical examinations of how the field‐effect mobility depends on gate capacitance have not been presented yet. Here, a systematic analysis of the field‐effect mobility on the gate capacitances in the solution‐processed OS TFTs is presented, where the multiple‐trapping‐and‐release and hopping percolation mechanism are used to describe the electrical conductivity of the nanocrystalline and amorphous OSs, respectively. An intuitive single‐piece expression showing how the field‐effect mobility depends on gate capacitance is developed based on the aforementioned mechanisms. The field‐effect mobility, depending on the gate capacitances, of the fabricated ZnO and ZnSnO TFTs clearly follows the theoretical prediction. In addition, the way in which the gate insulator properties (e.g., gate capacitance or dielectric constant) affect the field‐effect mobility maximum in the nanocrystalline ZnO and amorphous ZnSnO TFTs are investigated.     

High‐Mobility and Low Turn‐On Voltage n‐Channel OTFTs Based on a Solution‐Processable Derivative of Naphthalene Bisimide

In organic electronics solution‐processable n‐channel field‐effect transistors (FETs) matching the parameters of the best p‐channel FETs are needed. Progress toward the fabrication of such devices is strongly impeded by a limited number of suitable organic semiconductors as well as by the lack of processing techniques that enable strict control of the supramolecular organization in the deposited layer. Here, the use of N,N′‐bis(4‐n‐butylphenyl)‐1,4,5,8‐naphthalenetetracarboxylic‐1,4:5,8‐bisimide (NBI‐4‐n‐BuPh) for fabrication of n‐channel FETs is described. The unidirectionally oriented crystalline layers of NBI‐4‐n‐BuPh are obtained by the zone‐casting method under ambient conditions. Due to the bottom‐contact, top‐gate configuration used, the gate dielectric, Parylene C, also acts as a protective layer. This, together with a sufficiently low LUMO level of NBI‐4‐n‐BuPh allows the fabrication and operation of these novel n‐channel transistors under ambient conditions. The high order of the NBI‐4‐n‐BuPh molecules in the zone‐cast layer and high purity of the gate dielectric yield good performance of the transistors.     

Insulator Polarization Mechanisms in Polyelectrolyte‐Gated Organic Field‐Effect Transistors

Electrolyte‐gated organic field‐effect transistors (OFETs) hold promise for robust printed electronics operating at low voltages. The polarization mechanism of thin solid electrolyte films, the gate insulator in such OFETs, is still unclear and appears to limit the transient current characteristics of the transistors. Here, the polarization response of a thin proton membrane, a poly(styrenesulfonic acid) film, is controlled by varying the relative humidity. The formation of the conducting transistor channel follows the polarization of the polyelectrolyte, such that the drain transient current characteristics versus the time are rationalized by three different polarization mechanisms: the dipolar relaxation at high frequencies, the ionic relaxation (migration) at intermediate frequencies, and the electric double‐layer formation at the polyelectrolyte interfaces at low frequencies. The electric double layers of polyelectrolyte capacitors are formed in ～1 µs at humid conditions and an effective capacitance per area of 10 µF cm^?2 is obtained at 1 MHz, thus suggesting that this class of OFETs might operate at up to 1 MHz at 1 V.     

High‐Speed,Low‐Voltage,and Environmentally Stable Operation of Electrochemically Gated Zinc Oxide Nanowire Field‐Effect Transistors

Single‐crystal, 1D nanostructures are well known for their high mobility electronic transport properties. Oxide‐nanowire field‐effect transistors (FETs) offer both high optical transparency and large mechanical conformability which are essential for flexible and transparent display applications. Whereas the “on‐currents” achieved with nanowire channel transistors are already sufficient to drive active matrix organic light emitting diode (AMOLED) displays; it is shown here that incorporation of electrochemical‐gating (EG) to nanowire electronics reduces the operation voltage to ≤2 V. This opens up new possibilities of realizing flexible, portable, transparent displays that are powered by thin film batteries. A composite solid polymer electrolyte (CSPE) is used to obtain all‐solid‐state FETs with outstanding performance; the field‐effect mobility, on/off current ratio, transconductance, and subthreshold slope of a typical ZnO single‐nanowire transistor are 62 cm²/Vs, 10⁷, 155 μS/μm and 115 mV/dec, respectively. Practical use of such electrochemically‐gated field‐effect transistor (EG FET) devices is supported by their long‐term stability in air. Moreover, due to the good conductivity (≈10^?2 S/cm) of the CSPE, sufficiently high switching speed of such EG FETs is attainable; a cut‐off frequency in excess of 100 kHz is measured for in‐plane FETs with large gate‐channel distance of >10 μm. Consequently, operation speeds above MHz can be envisaged for top‐gate transistor geometries with insulator thicknesses of a few hundreds of nanometers. The solid polymer electrolyte developed in this study has great potential in future device fabrication using all‐solution processed and high throughput techniques.     

Dual‐Gate Organic Field‐Effect Transistors as Potentiometric Sensors in Aqueous Solution

Buried electrodes and protection of the semiconductor with a thin passivation layer are used to yield dual‐gate organic transducers. The process technology is scaled up to 150‐mm wafers. The transducers are potentiometric sensors where the detection relies on measuring a shift in the threshold voltage caused by changes in the electrochemical potential at the second gate dielectric. Analytes can only be detected within the Debye screening length. The mechanism is assessed by pH measurements. The threshold voltage shift depends on pH as ΔV_th = (C_top/C_bottom) × 58 mV per pH unit, indicating that the sensitivity can be enhanced with respect to conventional ion‐sensitive field‐effect transistors (ISFETs) by adjusting the ratio of the top and bottom gate capacitances. Remaining challenges and opportunities are discussed.     

Fully Patterned Low‐Voltage Transparent Metal Oxide Transistors Deposited Solely by Chemical Spray Pyrolysis

All‐inorganic transparent thin‐film transistors deposited solely by the solution processing method of spray pyrolysis are reported. Different precursor materials are employed to create conducting and semiconducting species of ZnO acting as electrodes and active channel material, respectively, as well as zirconium oxide as gate dielectric layer. Additionally, a simple stencil mask system provides sufficient resolution to realize the necessary geometric patterns. As a result, fully functional low‐voltage n‐type transistors with a mobility of 0.18 cm² V^?1 s^?1 can be demonstrated via a technique that bears the potential for upscaling. A detailed microscopic evaluation of the channel region by electron diffraction, high‐resolution and analytical TEM confirms the layer stacking and provides detailed information on the chemical composition and nanocrystalline nature of the individual layers.     

Solution‐Processed Zinc Oxide as High‐Performance Air‐Stable Electron Injector in Organic Ambipolar Light‐Emitting Field‐Effect Transistors

Electron injection from the source–drain electrodes limits the performance of many n‐type organic field‐effect transistors (OFETs), particularly those based on organic semiconductors with electron affinities less than 3.5 eV. Here, it is shown that modification of gold source–drain electrodes with an overlying solution‐deposited, patterned layer of an n‐type metal oxide such as zinc oxide (ZnO) provides an efficient electron‐injecting contact, which avoids the use of unstable low‐work‐function metals and is compatible with high‐resolution patterning techniques such as photolithography. Ambipolar light‐emitting field‐effect transistors (LEFETs) based on green‐light‐emitting poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) and blue‐light‐emitting poly(9,9‐dioctylfluorene) (F8) with electron‐injecting gold/ZnO and hole‐injecting gold electrodes show significantly lower electron threshold voltages and several orders of magnitude higher ambipolar currents, and hence light emission intensities, than devices with bare gold electrodes. Moreover, different solution‐deposited metal oxide injection layers are compared. By spin‐coating ZnO from a low‐temperature precursor, processing temperatures could be reduced to 150 °C. Ultraviolet photoemission spectroscopy (UPS) shows that the improvement in transistor performance is due to reduction of the electron injection barrier at the interface between the organic semiconductor and ZnO/Au compared to bare gold electrodes.     

Printed Sub‐2 V Gel‐Electrolyte‐Gated Polymer Transistors and Circuits

The fabrication and characterization of printed ion‐gel‐gated poly(3‐hexylthiophene) (P3HT) transistors and integrated circuits is reported, with emphasis on demonstrating both function and performance at supply voltages below 2 V. The key to achieving fast sub‐2 V operation is an unusual gel electrolyte based on an ionic liquid and a gelating block copolymer. This gel electrolyte serves as the gate dielectric and has both a short polarization response time (<1 ms) and a large specific capacitance (>10 µF cm^?2), which leads simultaneously to high output conductance (>2 mS mm^?1), low threshold voltage (<1 V) and high inverter switching frequencies (1–10 kHz). Aerosol‐jet‐printed inverters, ring oscillators, NAND gates, and flip‐flop circuits are demonstrated. The five‐stage ring oscillator operates at frequencies up to 150 Hz, corresponding to a propagation delay of 0.7 ms per stage. These printed gel electrolyte gated circuits compare favorably with other reported printed circuits that often require much larger operating voltages. Materials factors influencing the performance of the devices are discussed.     

High Performance Indium‐Gallium‐Zinc Oxide Thin Film Transistor via Interface Engineering

Solution‐processed indium‐gallium‐zinc oxide (IGZO) thin film transistors (TFTs) have become well known in recent decades for their promising commercial potential. However, the unsatisfactory performance of small‐sized IGZO TFTs is limiting their applicability. To address this issue, this work introduces an interface engineering method of bi‐functional acid modification to regulate the interfaces between electrodes and the channels of IGZO TFTs. This method increases the interface oxygen vacancy concentration and reduces the surface roughness, resulting in higher mobility and enhanced contact at the interfaces. The TFT devices thus treated display contact resistance reduction from 9.1 to 2.3 kΩmm, as measured by the gated four‐probe method, as well as field‐effect mobility increase from 1.5 to 4.5 cm² (V s)^?1. Additionally, a 12 × 12 organic light emitting diode display constructed using the acid modified IGZO TFTs as switching and driving elements demonstrate the applicability of these devices.     

Highly Sensitive Glucose Biosensors Based on Organic Electrochemical Transistors Using Platinum Gate Electrodes Modified with Enzyme and Nanomaterials

Organic electrochemical transistors with glucose oxidase‐modified Pt gate electrodes are successfully used as highly sensitive glucose sensors. The gate electrodes are modified with nanomaterials (multi‐wall carbon nanotubes or Pt nanoparticles) for the first time, which results in a dramatic improvement in the sensitivity of the devices. The detection limit of the device modified with Pt nanoparticles on the gate electrode is about 5 nM, which is three orders of magnitude better than a device without the nanoparticles. The improvement of the device performance can be attributed to the excellent electrocatalytic properties of the nanomaterials and more effective immobilization of enzyme on the gate electrodes. Based on the same principle, many other types of enzyme sensors with high sensitivity and low cost are expected to be realized by modifying the gate electrodes of organic electrochemical transistors with specific enzymes and nanomaterials.