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.     

Schottky‐Barrier‐Controllable Graphene Electrode to Boost Rectification in Organic Vertical P–N Junction Photodiodes

Monolayer graphene is used as an electrode to develop novel electronic device architectures that exploit the unique, atomically thin structure of the material with a low density of states at its charge neutrality point. For example, a single semiconductor layer stacked onto graphene can provide a semiconductor–electrode junction with a tunable injection barrier, which is the basis for a primitive transistor architecture known as the Schottky barrier field‐effect transistor. This work demonstrates the next level of complexity in a vertical graphene–semiconductor architecture. Specifically, an organic vertical p‐n junction (p‐type pentacene/n‐type N,N′‐dioctyl‐3,4,9,10‐perylenedicarboximide (PTCDI‐C₈)) on top of a graphene electrode constituting a novel gate‐tunable photodiode device structure is fabricated. The model device confirms that controlling the Schottky barrier height at the pentacene–graphene junction can (i) suppress the dark current density and (ii) enhance the photocurrent of the device, both of which are critical to improve the performance of a photodiode.     

Strain Modulation in Graphene/ZnO Nanorod Film Schottky Junction for Enhanced Photosensing Performance

Strain modulation in flexible semiconductor heterojunctions has always been considered as an effective way to modulate the performance of nanodevices. In this work, a graphene/ZnO nanorods film Schottky junction has been constructed. It shows considerable responsivity and fast on‐off switch to the UV illumination. Through utilizing the piezopotential induced by the atoms displacement in ZnO under the compressive strain, 17% enhanced photosensing property is achieved in this hybrid structure when applying ?0.349% strain. This performance improvement can be ascribed to the Schottky barrier height modification by the strain‐induced piezopotential, which results in the facilitation of electron–hole separation in the graphene/ZnO interface. An energy band principle as well as a finite element analysis is proposed to understand this phenomenon. The results here provide a facile approach to boost the optoelectronic performance of graphene/ZnO heterostructure, which may also be applied to other Schottky junction based hybrid devices.     

Ionic Liquid Activation of Amorphous Metal‐Oxide Semiconductors for Flexible Transparent Electronic Devices

Amorphous metal‐oxide semiconductors offer the high carrier mobilities and excellent large‐area uniformity required for high performance, transparent, flexible electronic devices; however, a critical bottleneck to their widespread implementation is the need to activate these materials at high temperatures which are not compatible with flexible polymer substrates. The highly controllable activation of amorphous indium gallium zinc oxide semiconductor channels using ionic liquid gating at room temperature is reported. Activation is controlled by electric field‐induced oxygen migration across the ionic liquid‐semiconductor interface. In addition to activation of unannealed devices, it is shown that threshold voltages of a transistor can be linearly tuned between the enhancement and depletion modes. Finally, the first ever example of transparent flexible thin film metal oxide transistor on a polyamide substrate created using this simple technique is demonstrated. This study demonstrates the potential of field‐induced activation as a promising alternative to traditional postdeposition thermal annealing which opens the door to wide scale implementation into flexible electronic applications.     

All‐Metallic Vertical Transistors Based on Stacked Dirac Materials

It is an ongoing pursuit to use metal as a channel material in a field effect transistor. All metallic transistor can be fabricated from pristine semimetallic Dirac materials (such as graphene, silicene, and germanene), but the on/off current ratio is very low. In a vertical heterostructure composed by two Dirac materials, the Dirac cones of the two materials survive the weak interlayer van der Waals interaction based on density functional theory method, and electron transport from the Dirac cone of one material to the one of the other material is therefore forbidden without assistance of phonon because of momentum mismatch. First‐principles quantum transport simulations of the all‐metallic vertical Dirac material heterostructure devices confirm the existence of a transport gap of over 0.4 eV, accompanied by a switching ratio of over 10⁴. Such a striking behavior is robust against the relative rotation between the two Dirac materials and can be extended to twisted bilayer graphene. Therefore, all‐metallic junction can be a semiconductor and novel avenue is opened up for Dirac material vertical structures in high‐performance devices without opening their band gaps.     

Enhanced Field Ionization Enabled by Metal Induced Surface States on Semiconductor Nanotips

Recent progress in the realization of material structures with quantum confinement and high surface to volume ratio in nanoscale interwoven metal and semiconductor building blocks offers a strong potential to build highly functional nanodevices. Ultra‐sharp tips with distinct material dependent properties of metal and semiconductor exhibit important functionalities in devices including gas ionization sensors, field emission devices, and ion‐mobility spectrometry. Herein, a dramatically enhanced field ionization process and a device based on charged particle beams for which the geometrical and surface properties of the constituent semiconductor nanotips are engineered with controlled introduction of metallic impurities to realize close to three orders of magnitude reduction in the ionization electric‐field strength are described. Experimentally observed low voltage field ionization phenomenon is explained using the geometrical field enhancement, surface states induced by controlled introduction of metallic impurities, and polarizabilities of gas particles at the nanotips. The nanotips are employed to design field ionization gas sensors whose nanoscale pristine semiconductor tips are controllably decorated with atomic metal impurities to boost the electron tunneling properties under extremely low bias voltages. These devices also outperform their solid‐state macroscopic counterparts in terms of simplicity of their construction and higher selectivity.     

High Mobility WS2 Transistors Realized by Multilayer Graphene Electrodes and Application to High Responsivity Flexible Photodetectors

The electrical contact is one of the main issues preventing semiconducting 2D materials to fulfill their potential in electronic and optoelectronic devices. To overcome this problem, a new approach is developed here that uses chemical vapor deposition grown multilayer graphene (MLG) sheets as flexible electrodes for WS₂ field‐effect transistors. The gate‐tunable Fermi level, van der Waals interaction with the WS₂, and the high electrical conductivity of MLG significantly improve the overall performance of the devices. The carrier mobility of single‐layer WS₂ increases about a tenfold (50 cm² V^?1 s^?1 at room temperature) by replacing conventional Ti/Au metal electrodes (5 cm² V^?1 s^?1) with the MLG electrodes. Further, by replacing the conventional SiO₂ substrate with a thin (1 µm) parylene‐C flexible film as insulator, flexible WS₂ photodetectors that are able to sustain multiple bending stress tests without significant performance degradation are realized. The flexible photodetectors exhibited extraordinarily high gate‐tunable photoresponsivities, reaching values of 4500 A W^?1, and with very short (<2 ms) response time. The work of the heterostacked structure combining WS₂, graphene, and the very thin polymer film will find applications in various flexible electronics, such as wearable high‐performance optoelectronics devices.     

Ultraviolet‐Light‐Induced Reversible and Stable Carrier Modulation in MoS2 Field‐Effect Transistors

The tuning of charge carrier concentrations in semiconductor is necessary in order to approach high performance of the electronic and optoelectronic devices. It is demonstrated that the charge‐carrier density of single‐layer (SL), bilayer (BL), and few‐layer (FL) MoS₂ nanosheets can be finely and reversibly tuned with N₂ and O₂ gas in the presence of deep‐ultraviolet (DUV) light. After exposure to N₂ gas in the presence of DUV light, the threshold voltages of SL, BL, and FL MoS₂ field‐effect transistors (FETs) shift towards negative gate voltages. The exposure to N₂ gas in the presence of DUV light notably improves the drain‐to‐source current, carrier density, and charge‐carrier mobility for SL, BL, and FL MoS₂ FETs. Subsequently, the same devices are exposed to O₂ gas in the presence of DUV light for different periods and the electrical characteristics are completely recovered after a certain time. The doping by using the combination of N₂ and O₂ gas with DUV light provides a stable, effective, and facile approach for improving the performance of MoS₂ electronic devices.     

Direct Patterning of Metal Chalcogenide Semiconductor Materials

Lithography is one of the most widely used methods for cutting‐edge research and industrial applications, mainly owing to its ability to draw patterns in the micro and even nanoscale. However, the fabrication of semiconductor micro/nanostructures via conventional electron or optical lithography technologies often requires a time‐consuming multistep process and the use of expensive facilities. Herein, a low‐cost, high‐resolution, facile, and versatile direct patterning method based on metal–organic molecular precursors is reported. The ink‐based metal–organic precursors are found to operate as negative resists, with the material exposed by different methods (electron‐beam/laser/heat/ultraviolet (UV)) to render them insoluble in the development process. This technical process can deliver metal chalcogenide semiconductors with arbitrary 2D/3D patterns with sub‐50 nm resolution. Electron beam lithography, two‐photon absorption lithography, thermal scanning probe lithography, and UV photolithography are demonstrated for the direct patterning process. Different metal chalcogenide semiconductor nanodevices, such as photoconductive selenium‐doped Sb₂S₃ nanoribbons, p‐type PbS single‐nanowire field‐effect transistors, and p‐n junction CdS/Cu₂S nanowire solar cells, are fabricated by this method. This direct patterning technique is a versatile and simple micro/nanolithography technology with considerable potential for “lab‐on‐a‐chip” preparation of semiconductor devices.     

Single‐Electron Tunneling through Molecular Quantum Dots in a Metal‐Insulator‐Semiconductor Structure

A sigle‐electron tunneling (SET) in a metal‐insulator‐semiconductor (MIS) structure is demonstrated, in which C₆₀ and copper phthalocyanine (CuPc) molecules are embedded as quantum dots in the insulator layer. The SET is found to originate from resonant tunneling via the energy levels of the embedded molecules, (e.g., the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO)). These findings show that the threshold voltages for SET are tunable according to the energy levels of the molecules. Furthermore, SET is observable even near room temperature. The results suggest, together with the fact that these properties are demonstrated in a practical device configuration, that the integration of molecular dots into the Si‐MIS structure has considerable potential for achieving novel SET devices. Moreover, the attempt allows large‐scale integration of individual molecular functionalities.     

Versatile Graphene‐Promoting Photocatalytic Performance of Semiconductors: Basic Principles,Synthesis, Solar Energy Conversion,and Environmental Applications

Graphene‐semiconductor nanocomposites, considered as a kind of most promising photocatalysts, have shown remarkable performance and drawn significant attention in the field of photo‐driven chemical conversion using solar energy, due to the unique physicochemical properties of graphene. The photocatalytic enhancement of graphene‐based nanocomposites is caused by the reduction of the recombination of electron‐hole pairs, the extension of the light absorption range, increase of absorption of light intensity, enhancement of surface active sites, and improvement of chemical stability of photocatalysts. Recent progress in the photocatalysis development of graphene‐based nanocomposites is highlighted and evaluated, focusing on the mechanism of graphene‐enhanced photocatalytic activity, the understanding of electron transport, and the applications of graphene‐based photocatalysts on water splitting, degradation or oxidization of organic contaminants, photoreduction of CO₂ into renewable fuels, toxic elimination of heavy metal ions, and antibacterial applications.     

Control of Ambipolar and Unipolar Transport in Organic Transistors by Selective Inkjet‐Printed Chemical Doping for High Performance Complementary Circuits

The selective tuning of the operational mode from ambipolar to unipolar transport in organic field‐effect transistors (OFETs) by printing molecular dopants is reported. The field‐effect mobility (μ_FET) and onset voltage (V_on) of both for electrons and holes in initially ambipolar methanofullerene [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) OFETs are precisely modulated by incorporating a small amount of cesium fluoride (CsF) n‐type dopant or tetrafluoro‐tetracyanoquinodimethane (F4‐TCNQ) p‐type dopant for n‐channel or p‐channel OFETs either by blending or inkjet printing of the dopant on the pre‐deposited semiconductor. Excess carriers introduced by the chemical doping compensate traps by shifting the Fermi level (E_F) toward respective transport energy levels and therefore increase the number of mobile charges electrostatically accumulated in channel at the same gate bias voltage. In particular, n‐doped OFETs with CsF show gate‐voltage independent Ohmic injection. Interestingly, n‐ or p‐doped OFETs show a lower sensitivity to gate‐bias stress and an improved ambient stability with respect to pristine devices. Finally, complementary inverters composed of n‐ and p‐type PCBM OFETs are demonstrated by selective doping of the pre‐deposited semiconductor via inkjet printing of the dopants.     

Ionic Liquid‐Assisted Synthesis of TiO2–Carbon Hybrid Nanostructures for Lithium‐Ion Batteries

Building nanocomposite architectures based on nanocarbon materials (such as carbon nanotubes and graphene nanosheets) and metal‐oxide nanoparticles is of great interests for electrochemical energy storage. Here, an ionic‐liquid‐assisted strategy is presented to mediate the in situ growth of TiO₂ nanocrystals with controlled size on carbon nanotubes and graphene, and also reduce the modified carbon supports to recover the graphitic structure simultaneously. The as‐prepared nanocomposites exhibit a highly porous and robust structure with intimate coupling between TiO₂ nanocrystals and carbon supports, which offers facile ion and electron transport pathway as well as high mechanical stability. When evaluated as electrode materials for lithium‐ion batteries, the nanocomposites manifest high specific capacity, long cycling lifetime, and excellent rate capability, showing their promising application in high‐performance energy storage devices.     

Synergistic Use of Pyridine and Selenophene in a Diketopyrrolopyrrole‐Based Conjugated Polymer Enhances the Electron Mobility in Organic Transistors

To achieve semiconducting materials with high electron mobility in organic field‐effect transistors (OFETs), low‐lying energy levels (the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO)) and favorable molecular packing and ordering are two crucial factors. Here, it is reported that the incorporation of pyridine and selenophene into the backbone of a diketopyrrolopyrrole (DPP)‐based copolymer produces a high‐electron‐mobility semiconductor, PDPPy‐Se. Compared with analogous polymers based on other DPP derivatives and selenophene, PDPPy‐Se features a lower LUMO that can decrease the electron transfer barrier for more effective electron injection, and simultaneously a lower HOMO that, however, can increase the hole transfer barrier to suppress the hole injection. Combined with thermal annealing at 240 °C for thin film morphology optimization to achieve large‐scale crystallite domains with tight molecular packing for effective charge transport along the conducting channel, OFET devices fabricated with PDPPy‐Se exhibit an n‐type‐dominant performance with an electron mobility (μ_e) as high as 2.22 cm² V^?1 s^?1 and a hole/electron mobility ratio (μ_h/μ_e) of 0.26. Overall, this study demonstrates a simple yet effective approach to boost the electron mobility in organic transistors by synergistic use of pyridine and selenophene in the backbone of a DPP‐based copolymer.     

Growth of Large Crystalline Grains of Vanadyl‐Phthalocyanine without Epitaxy on Graphene

The performance of organic semiconductor thin films in electronic devices is related to their crystal structure and morphology, with charge transport mobility dependent on the degree of crystallinity and on the crystallographic orientation. Here organic molecular beam deposition of vanadyl phthalocyanine is studied on graphene and it is shown that crystalline grains up to several micrometers across can be formed at substrate temperatures of 155 °C, compared to room temperature grain sizes of ≈30 nm. Transmission electron microscopy confirms the presence of long range order at elevated substrate temperatures and reveals that the molecules are stacked in an edge‐on orientation, but are not epitaxially aligned to the graphene. The crystalline grain sizes are significantly larger on graphene than on disordered substrates such as graphene oxide and silicon oxide. The effect on charge transport is probed by conducting atomic force microscopy, with the high temperature films on graphene showing increased mobility and uniformity and decreased trap density. These results illustrate an important advantage for the integration of graphene electrodes with organic semiconductor devices: the homogeneous surface of graphene results in high diffusion and low nucleation rates for thin film growth, encouraging the formation of highly crystalline films even with nonepitaxial growth.     

Tuning the Excitonic States in MoS2/Graphene van der Waals Heterostructures via Electrochemical Gating

The behavior of excitons in van der Waals (vdWs) heterostructures depends on electron–electron interactions and charge transfer at the hetero‐interface. However, what still remains to be unraveled is to which extent the carrier densities of both counterparts and the band alignment in the vdWs heterostructures determine the photoluminescence properties. Here, we systematically study the photoluminescence properties of monolayer MoS₂/graphene heterostructures by modulating the carrier densities and contact barrier at the interface via electrochemical gating. It is shown that the PL intensities of excitons can be tuned by more than two orders of magnitude, and a blue‐shift of the exciton peak of up to 40 meV is observed. By extracting the carrier density of MoS₂ using an electric potential distribution model, and the Schottky barrier using first‐principle calculations, we find that the controllable carrier density in MoS₂ plays a dominant role in the PL tuning at negative gate bias, whereas the interlayer relaxation of excitons induced by the Schottky barrier has a major contribution at positive gate bias. This is further verified by controlling the tunneling barrier and screening field across MoS₂ by inserting self‐assembled monolayers (SAMs) at the interface. These findings will benefit to better understand the effect of many‐body interactions and hetero‐interfaces on the optical and optoelectronic properties in vdWs heterostructures.     

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.     

High-voltage junction-gate field-effect transistor with recessed gates

A new recessed-gate structure for vertical-channel junction field-effect transistors (JFET's) is described together with a self-aligned gate-source process developed to fabricate these devices. Using this technology, devices with groove depths ranging from 8 to 18 µm have been fabricated. The characteristics of these devices is described as a function of the groove depth. It has been found that the devices display pentode-like characteristics at low gate voltages and triode-like characteristics at high gate voltages. The blocking gain has been found to increase with groove depth. However, this is accompanied by an increase in the on-resistance and a decrease in the saturated drain current. Devices with gate breakdown voltages of up to 600 V have been fabricated with the recessed-gate structure. These high-voltage field-effect transistors (FET's) have a unity power gain cutoff frequency of 600 MHz and gate turn-off times of less than 25 ns.     

CdS Nanoribbon‐Based Resistive Switches with Ultrawidely Tunable Power by Surface Charge Transfer Doping

Traditional metal–insulator–metal (MIM)‐based resistive switches (RS) possess a high operating current, which can be read directly without an amplifier yet will inevitably produce large power consumption. Rational control of the energy consumption of RS devices is surely desirable to achieve the energy‐efficient purpose in a variety of practical applications. Here a surface charge transfer doping (SCTD) strategy is reported to manipulate the operating current as well as power consumption of the RS devices by using doped CdS nanoribbon (NR) as a rheostat. By controlling the concentration of surface dopant of MoO₃, the conductivity of doped CdS NR can be tuned in a wide range of nine orders of magnitude, showing the transition from insulator to semiconductor and to conductor. On the basis of CdS NRs with controllable conductivity, the as‐fabricated RS devices exhibit an ultrawidely tunable‐power consumption from 1 nW, the lowest value reported so far, to 0.1 mW, which is close to the typical values of MIM‐based RS devices. In view of the high controllability of the SCTD method, this work opens up unique opportunities for future energy‐efficient, performance‐tunable, and multifunctional RS devices based on semiconductor nanostructures.