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.     

Gate‐Controlled Energy Barrier at a Graphene/Molecular Semiconductor Junction

The formation of an energy‐barrier at a metal/molecular semiconductor junction is a universal phenomenon which limits the performance of many molecular semiconductor‐based electronic devices, from field‐effect transistors to light‐emitting diodes. In general, a specific metal/molecular semiconductor combination of materials leads to a fixed energy‐barrier. However, in this work, a graphene/C₆₀ vertical field‐effect transistor is presented in which control of the interfacial energy‐barrier is demonstrated, such that the junction switches from a highly rectifying diode at negative gate voltages to a highly conductive nonrectifying behavior at positive gate voltages and at room temperature. From the experimental data, an energy‐barrier modulation of up to 660 meV, a transconductance of up to five orders of magnitude, and a gate‐modulated photocurrent are extracted. The ability to tune the graphene/molecular semiconductor energy‐barrier provides a promising route toward novel, high performance molecular devices.     

Photo‐Stable Organic Thin‐Film Transistor Utilizing a New Indolocarbazole Derivative for Image Pixel and Logic Applications

Small molecule pentacene layer has been a representative among many organic thin‐film transistor (OTFT) channels with decent p‐type mobilities, but it is certainly light‐sensitive due to its relatively small highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) gap (1.85 eV). Although a few other small molecule‐based layers have been reported later, their photo‐stabilities or related device applications have hardly been addressed. Here, a new photostable organic layer is reported, heptazole (C₂₆H₁₆N₂), which has almost the same HOMO level as that of pentacene but with a higher HOMO‐LUMO gap (≈2.95 eV). This heptazole OTFT displays a decent mobility comparable to that of conventional amorphous Si TFTs, showing good photostability unlike pentacene OTFTs. An image pixel driving the photostable heptazole OTFT connected to a pentacene/Al Schottky photodiode is demonstrated. This heptazole OTFT also conveniently forms a logic inverter coupled with a pentacene OTFT, sharing Au for source/drain.     

Analog Circuit Applications Based on All‐2D Ambipolar ReSe2 Field‐Effect Transistors

Complementary circuits based on 2D materials show great promise for next‐generation electronics. An ambipolar all‐2D ReSe₂ field‐effect transistor (FET) with a hexagonal boron nitride gate dielectric is fabricated and its electronic characteristics are comprehensively studied by temperature dependence and noise measurements. Ambipolar transfer characteristics are achieved owing to the tunable Fermi level of the graphene contact and negligible and 30 meV Schottky barrier heights for the n‐ and p‐channel regimes, respectively. An inverter is also fabricated to demonstrate ambipolar ReSe₂ FET operation in a logic circuit. Furthermore, a p/n switchable unipolar FET is designed and shows potential for building complimentary circuits from a signal device. This work demonstrates the potential of all‐2D ReSe₂ FETs and makes available new approaches for designing next‐generation devices.     

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.     

Plasmon‐Induced Sub‐Bandgap Photodetection with Organic Schottky Diodes

Organic materials for near‐infrared (NIR) photodetection are in the focus for developing organic optical‐sensing devices. The choice of materials for bulk‐type organic photodetectors is limited due to effects like high nonradiative recombination rates for low‐gap materials. Here, an organic Schottky barrier photodetector with an integrated plasmonic nanohole electrode is proposed, enabling structure‐dependent, sub‐bandgap photodetection in the NIR. Photons are detected via internal photoemission (IPE) process over a metal/organic semiconductor Schottky barrier. The efficiency of IPE is improved by exciting localized surface plasmon resonances, which are further enhanced by coupling to an out‐of‐plane Fabry–Pérot cavity within the metal/organic/metal device configuration. The device allows large on/off ratio (>1000) and the selective control of individual pixels by modulating the Schottky barrier height. The concept opens up new design and application possibilities for organic NIR photodetectors.     

Experimental and numerical analysis of channel-length-dependent electrical properties in bottom-gate,bottom-contact organic thin-film transistors with Schottky contact

Channel length dependence of field-effect mobility and source/drain parasitic resistance in pentacene thin-film transistors with a bottom-gate, bottom-contact configuration was investigated. Schottky barrier effect such as nonlinear behaviors in transistor output characteristics appeared and became more prominent for shorter channel length less than 10 μm, raising some concerns for a simple utilization of conventional parameter extraction methods. Therefore the gate-voltage-dependent hole mobility and the source/drain parasitic resistance in the pentacene transistors were evaluated with the aid of device simulation accounting for Schottky contact with a thermionic field emission model. The hole mobility in the channel region shows smaller values with shorter channel length even after removing the influence of Schottky barrier, suggesting that some disordered semiconductor layers with low carrier mobility exist near the contact electrode. This experimental data analysis with the simulation enables us to discuss and understand in detail the operation mechanism of bottom-gate, bottom-contact transistors by considering properly each process of charge carrier injection, carrier flow near the contact region, and actual channel transport.     

Semiconductor‐Based Photoelectrochemical Water Splitting at the Limit of Very Wide Depletion Region

In semiconductor‐based photoelectrochemical (PEC) water splitting, carrier separation and delivery largely relies on the depletion region formed at the semiconductor/water interface. As a Schottky junction device, the trade‐off between photon collection and minority carrier delivery remains a persistent obstacle for maximizing the performance of a water splitting photoelectrode. Here, it is demonstrated that the PEC water splitting efficiency for an n‐SrTiO₃ (n‐STO) photoanode is improved very significantly despite its weak indirect band gap optical absorption (α < 10⁴ cm^?1), by widening the depletion region through engineering its doping density and profile. Graded doped n‐SrTiO₃ photoanodes are fabricated with their bulk heavily doped with oxygen vacancies but their surface lightly doped over a tunable depth of a few hundred nanometers, through a simple low temperature reoxidation technique. The graded doping profile widens the depletion region to over 500 nm, thus leading to very efficient charge carrier separation and high quantum efficiency (>70%) for the weak indirect transition. This simultaneous optimization of the light absorption, minority carrier (hole) delivery, and majority carrier (electron) transport by means of a graded doping architecture may be useful for other indirect band gap photocatalysts that suffer from a similar problem of weak optical absorption.     

A Generic Conversion Strategy: From 2D Metal Carbides (MxCy) to M‐Self‐Doped Graphene toward High‐Efficiency Energy Applications

This study first presents a subtle thermal‐chlorination strategy for a universal transformation of abundant 2D metal carbides (M_xC_y, e.g., Cr₃C₂, Mo₂C, NbC, and VC) to 2D graphene and M‐self‐doped graphene (MG). The as‐obtained MG endows a transparent sheet architecture of one to four atomic layers. Simultaneously, MG with different M amounts is synthesized by tuning the chlorination parameters. Among them, the novel and representative Cr‐self‐doped graphene with optimal Cr amount (4.81 at%) demonstrates the outstanding electrochemical performance. It presents an energy density of 686 W h per kg electrode and a power density of more than 391 W per kg electrode as anode material of Li ion batteries, and four‐fold activity against the commercial iridium oxide electrode toward oxygen evolution reaction as well as a comparable oxygen reduction reaction performance to the commercial platinum catalyst. Moreover, this method is readily scalable to produce graphene and MG electrode materials on industrial levels.     

Influence of Electric Field on Microstructures of Pentacene Thin‐Films in Field‐Effect Transistors

We report on electric‐field‐induced irreversible structural modifications in pentacene thin films after long‐term operation of organic field‐effect transistor (OFET) devices. Micro‐Raman spectroscopy allows for the analysis of the microstructural modifications of pentacene in the small active channel of OFET during device operation. The results suggest that the herringbone packing of pentacene molecules in a solid film is affected by an external electric field, particularly the source‐to‐drain field that parallels the a–b lattice plane. The analysis of vibrational frequency and Davydov splitting in the Raman spectra reveals a singular behavior suggesting a reduced separation distance between pentacene molecules after long‐term operations and, thus, large intermolecular interactions. These results provide evidence for improved OFET performance after long‐term operation, related to the microstructures of organic semiconductors. It is known that the application of large electric fields alters the semiconductor properties of the material owing to the generation of defects and the trapping of charges. However, we first suggest that large electric fields may alter the molecular geometry and further induce structural phase transitions in the pentacene films. These results provide a basis for understanding the improved electronic properties in test devices after long‐term operations, including enhanced field‐effect mobility, improved on/off current ratio, sharp sub‐threshold swing, and a slower decay rate in the output drain current. In addition, the effects of source‐to‐drain electric field, gate electric field, current and charge carriers, and thermal annealing on the pentacene films during OFET operations are discussed.     

High Responsivity and Response Speed Single‐Layer Mixed‐Cation Lead Mixed‐Halide Perovskite Photodetectors Based on Nanogap Electrodes Manufactured on Large‐Area Rigid and Flexible Substrates

Mixed‐cation lead mixed‐halide perovskites are employed as the photoactive material in single‐layer solution‐processed photodetectors fabricated with coplanar asymmetric nanogap Al–Au and indium tin oxide–Al electrodes. The nanogap electrodes, bearing an interelectrode distance of ≈10 nm, are patterned via adhesion lithography, a simple, low‐cost, and high‐throughput technique. Different electrode shapes and sizes are demonstrated on glass and flexible plastic substrates, effectively engineering the device architecture, and, along with perovskite film and material optimization, paving the way toward devices with tunable operational characteristics. The optimized coplanar nanogap junction perovskite photodetectors show responsivities up to 33 A W^?1, specific detectivity on the order of 10¹¹ Jones, and response times below 260 ns, while retaining a low dark current (0.3 nA) under ?2 V reverse bias. These values outperform the vast majority of perovskite photodetectors reported so far, while avoiding the complicated fabrication steps involved in conventional multilayer device structures. This work highlights the promising potential of the proposed asymmetric nanogap electrode architecture for application in the field of flexible optoelectronics.     

p‐Type Beta‐Silver Vanadate Nanoribbons for Nanoelectronic Devices with Tunable Electrical Properties

β‐AgVO₃, as a stable phase and a typical silver vanadium oxide, has performed special ionic and electrical properties. The construction of nanoelectronic devices based on ultralong β‐AgVO₃ nanoribbons (NRs) is reported, including nano‐field‐effect transistor (nano‐FET) and nano‐Schottky barrier diode (nano‐SBD). Owing to the specific channel structure and ion conductivity, the nano‐FET exhibits typical p‐type semiconductor characteristics and the nano‐SBD with Al contacts performs a prominent rectifying behavior with an on/off ratio of up to 10³. Besides, tunable electrical transport properties can be achieved by tailoring the material properties, and it is demonstrated that the bridging NR numbers and diameters have a positive effect on electrical transport properties, while a complex variation trend is observed in the case of surface modification by photo‐irradiation. Electron spin resonance (ESR) spectrum further illuminates that the induced vacancies play an important role on the electrical transport properties of β‐AgVO₃ nanoribbons. Easy access to the ultralong β‐AgVO₃ NRs makes them a promising candidate for potential applications in nanoelectronic devices.     

Ultrahigh Speed and Broadband Few‐Layer MoTe2/Si 2D–3D Heterojunction‐Based Photodiodes Fabricated by Pulsed Laser Deposition

2D transition metal dichalcogenides are promising candidates for high‐performance photodetectors. However, the relatively low response speed as well as the complex transfer process hinders their wide applications. Herein, for the first time, the fabrication of a few‐layer MoTe₂/Si 2D–3D vertical heterojunction for high‐speed and broadband photodiodes by a pulsed laser deposition technique is reported. Owing to the high junction quality, ultrathin MoTe₂ film thickness, and unique vertical n–n heterojunction structure, the photodiode exhibits excellent device performance in terms of a high responsivity of 0.19 A W^?1 and a large detectivity of 6.8 × 10¹³ Jones. The device is also capable of detecting a broadband light with wavelength spanning from 300 to 1800 nm. More importantly, the device possesses an ultrahigh response speed up to 150 ns with a 3‐dB electrical bandwidth approaching 0.12 GHz. This work paves the way toward the fabrication of novel 2D–3D heterojunctions for high‐performance, ultrafast photodetectors.     

Orders‐of‐Magnitude Reduction of the Contact Resistance in Short‐Channel Hot Embossed Organic Thin Film Transistors by Oxidative Treatment of Au‐Electrodes

In this study we report on the optimization of the contact resistance by surface treatment in short‐channel bottom‐contact OTFTs based on pentacene as semiconductor and SiO₂ as gate dielectric. The devices have been fabricated by means of nanoimprint lithography with channel lengths in the range of 0.3 μm < L < 3.0 μm. In order to reduce the contact resistance the Au source‐ and drain‐contacts were subjected to a special UV/ozone treatment, which induced the formation of a thin AuO_x layer. It turned out, that the treatment is very effective (i) in decreasing the hole‐injection barrier between Au and pentacene and (ii) in improving the morphology of pentacene on top of the Au contacts and thus reducing the access resistance of carriers to the channel. Contact resistance values as low as 80 Ω cm were achieved for gate voltages well above the threshold. In devices with untreated contacts, the charge carrier mobility shows a power‐law dependence on the channel length, which is closely related to the contact resistance and to the grain‐size of the pentacene crystallites. Devices with UV/ozone treated contacts of very low resistance, however, exhibit a charge carrier mobility in the range of 0.3 cm² V^–1 s^–1 < μ < 0.4 cm² V^–1 s^–1 independent of the channel length.     

A New Carbazole‐Constructed Hyperbranched Polymer: Convenient One‐Pot Synthesis,Hole‐Transporting Ability,and Field‐Effect Transistor Properties

A new hyperbranched polymer ( HB‐car ), constructed fully by carbazole moieties, is successfully synthesized through a one‐pot Suzuki coupling reaction. The resultant polymer is well‐characterized, and its hole‐transporting ability is studied carefully. The device, in which HB‐car is utilized as a hole‐transporting layer and tris‐(8‐hydroxyquinoline) aluminum as an electron‐emitting layer as well as electron‐transporting layer, gives a much higher efficiency (3.05 cd A^–1), than that of a poly(N‐vinylcarbazole) based device (2.19 cd A^–1) under similar experimental conditions. The remarkable performance is attributed to its low energy barrier and enhanced hole‐drifting ability in the HB‐car based device. In addition, for the first time, a field‐effect transistor (FET) based on the hyperbranched polymer is fabricated, and the organic FET device shows that HB‐car is a typical p‐type FET material with a saturation mobility of 1 × 10^–5 cm² V^–1 s^–1, a threshold voltage of –47.1 V, and an on‐to‐off current ratio of 10³.     

Non‐volatile Ferroelectric Poly(vinylidene fluoride‐co‐trifluoroethylene) Memory Based on a Single‐Crystalline Tri‐isopropylsilylethynyl Pentacene Field‐Effect Transistor

A new type of nonvolatile ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) (P(VDF‐TrFE)) memory based on an organic thin‐film transistor (OTFT) with a single crystal of tri‐isopropylsilylethynyl pentacene (TIPS‐PEN) as the active layer is developed. A bottom‐gate OTFT is fabricated with a thin P(VDF‐TrFE) film gate insulator on which a one‐dimensional ribbon‐type TIPS‐PEN single crystal, grown via a solvent‐exchange method, is positioned between the Au source and drain electrodes. Post‐thermal treatment optimizes the interface between the flat, single‐crystalline ab plane of TIPS‐PEN and the polycrystalline P(VDF‐TrFE) surface with characteristic needle‐like crystalline lamellae. As a consequence, the memory device exhibits a substantially stable source–drain current modulation with an ON/OFF ratio hysteresis greater than 10³, which is superior to a ferroelectric P(VDF‐TrFE) OTFT that has a vacuum‐evaporated pentacene layer. Data retention longer than 5 × 10⁴ s is additionally achieved in ambient conditions by incorporating an interlayer between the gate electrode and P(VDF‐TrFE) thin film. The device is environmentally stable for more than 40 days without additional passivation. The deposition of a seed solution of TIPS‐PEN on the chemically micropatterned surface allows fabrication arrays of TIPS‐PEN single crystals that can be potentially useful for integrated arrays of ferroelectric polymeric TFT memory.     

2,7‐Carbazolenevinylene‐Based Oligomer Thin‐Film Transistors: High Mobility Through Structural Ordering

We have fabricated organic field‐effect transistors based on thin films of 2,7‐carbazole oligomeric semiconductors 1,4‐bis(vinylene‐(N‐hexyl‐2‐carbazole))phenylene (CPC), 1,4‐bis(vinylene‐(N′‐methyl‐7′‐hexyl‐2′‐carbazole))benzene (RCPCR), N‐hexyl‐2,7‐bis(vinylene‐(N‐hexyl‐2‐carbazole))carbazole (CCC), and N‐methyl‐2,7‐bis(vinylene‐(7‐hexyl‐N‐methyl‐2‐carbazole))carbazole (RCCCR). The organic semiconductors are deposited by thermal evaporation on bare and chemically modified silicon dioxide surfaces (SiO₂/Si) held at different temperatures varying from 25 to 200 °C during deposition. The resulting thin films have been characterized using UV‐vis and Fourier‐transform infrared spectroscopies, scanning electron microscopy, and X‐ray diffraction, and the observed top‐contact transistor performances have been correlated with thin‐film properties. We found that these new π‐conjugated oligomers can form highly ordered structures and reach high hole mobilities. Devices using CPC as the active semiconductor have exhibited mobilities as high as 0.3 cm² V^–1 s^–1 with on/off current ratios of up to 10⁷. These features make CPC and 2,7‐carbazolenevinylene‐based oligomers attractive candidates for device applications.     

Preparation and Memory Performance of a Nanoaggregated Dispersed Red 1‐Functionalized Poly (N‐vinylcarbazole) Film via Solution‐Phase Self‐Assembly

A nanoaggregated dispersed red 1‐grafted poly(N‐vinylcarbazole) (abbreviated PVDR) is self‐assembled via π–π stacking interactions of the carbazole groups in the polymer system after adding a solution of PVDR in N,N‐dimethylformamide to dichloromethane. Upon self‐assembly, the nanoaggregated PVDR film displays helical columnar stacks with large grain sizes, whereas a non‐aggregated PVDR film exhibits an amorphous morphology with smaller grain size. A write‐once read‐many‐times (WORM) memory device is shown whereby a pre‐assembled solution of PVDR is spin‐coated as the active layer and is sandwiched between an aluminum electrode and an indium‐tin‐oxide (ITO) electrode. This device shows very good memory performance, with an ON/OFF current ratio of more than 10⁵ and a low misreading rate through the precise control of the ON and OFF states. The stability of the nanoaggregated PVDR device is much higher than that of the non‐nanoaggregated PVDR device. This difference in device stability under constant voltage stress can be mainly attributed to the difference in the film crystallinity and surface morphology. No degradation in current density was observed for the ON‐ and OFF‐states after more than one hundred million (10⁸) continuous read cycles indicating that both states were insensitive to the read cycles. These results render the nanoaggregated PVDR polymer as promising components for high‐performance polymer memory devices.     

Bilayer tellurene-metal interfaces

Tellurene, an emerging two-dimensional chain-like semiconductor, stands out for its high switch ratio, carrier mobility and excellent stability in air. Directly contacting the 2D semiconductor materials with metal electrodes is a feasible doping means to inject carriers. However, Schottky barrier often arises at the metal–semiconductors interface, impeding the transport of carriers. Herein, we investigate the interfacial properties of BL tellurene by contacting with various metals including graphene by using ab initio calculations and quantum transport simulations. Vertical Schottky barriers take place in Ag, Al, Au and Cu electrodes according to the maintenance of the noncontact tellurene layer band structure. Besides, a p-type vertical Schottky contact is formed due to the van der Waals interaction for graphene electrode. As for the lateral direction, p-type Schottky contacts take shape for bulk metal electrodes(hole Schottky barrier heights(SBHs) ranging from 0.19 to 0.35 eV). Strong Fermi level pinning takes place with a pinning factor of 0.02. Notably, a desirable p-type quasi-Ohmic contact is developed for graphene electrode with a hole SBH of 0.08 eV. Our work sheds light on the interfacial properties of BL tellurene based transistors and could guide the experimental selections on electrodes.     

Self‐Assembled,Millimeter‐Sized TIPS‐Pentacene Spherulites Grown on Partially Crosslinked Polymer Gate Dielectric

Here, a highly crystalline and self‐assembled 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐Pentacene) thin films formed by simple spin‐coating for the fabrication of high‐performance solution‐processed organic field‐effect transistors (OFETs) are reported. Rather than using semiconducting organic small‐molecule–insulating polymer blends for an active layer of an organic transistor, TIPS‐Pentacene organic semiconductor is separately self‐assembled on partially crosslinked poly‐4‐vinylphenol:poly(melamine‐co‐formaldehyde) (PVP:PMF) gate dielectric, which results in a vertically segregated semiconductor‐dielectric film with millimeter‐sized spherulite‐crystalline morphology of TIPS‐Pentacene. The structural and electrical properties of TIPS‐Pentacene/PVP:PMF films have been studied using a combination of polarized optical microscopy, atomic force microscopy, 2D‐grazing incidence wide‐angle X‐ray scattering, and secondary ion mass spectrometry. It is finally demonstrated a high‐performance OFETs with a maximum hole mobility of 3.40 cm² V^?1 s^?1 which is, to the best of our knowledge, one of the highest mobility values for TIPS‐Pentacene OFETs fabricated using a conventional solution process. It is expected that this new deposition method would be applicable to other small molecular semiconductor–curable polymer gate dielectric systems for high‐performance organic electronic applications.