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.     

Improved Electrical Contact Properties of MoS2‐Graphene Lateral Heterostructure

2D materials have been extensively investigated in view of their excellent electrical/optical properties, with particular attention directed at the fabrication of vertical or lateral heterostructures. Although such heterostructures exhibit unexpected or enhanced properties compared to those of singly used 2D materials, their fabrication is challenged by the difficulty of realizing spatial control and large area integration. Herein, MoS₂ is grown on patterned graphene at variable temperatures, combining the concept of lateral heterostructure with chemical vapor deposition to realize large area growth with precise spatial control, and probe the spatial distribution of graphene and MoS₂ by a number of instrumental techniques. The prepared MoS₂‐graphene lateral heterostructure is employed to construct field effect transistors with graphene as the source/drain and MoS₂ as the channel, and the performance of these transistors (on/off ratio ≈10⁹, maximum field effect mobility = 8.5 cm² V^?1 s^?1) is shown to exceed that of their MoS₂‐only counterparts.     

Nonvolatile Ferroelectric Memory Effect in Ultrathin α‐In2Se3

High‐density memory is integral in solid‐state electronics. 2D ferroelectrics offer a new platform for developing ultrathin electronic devices with nonvolatile functionality. Recent experiments on layered α‐In₂Se₃ confirm its room‐temperature out‐of‐plane ferroelectricity under ambient conditions. Here, a nonvolatile memory effect in a hybrid 2D ferroelectric field‐effect transistor (FeFET) made of ultrathin α‐In₂Se₃ and graphene is demonstrated. The resistance of the graphene channel in the FeFET is effectively controllable and retentive due to the electrostatic doping, which stems from the electric polarization of the ferroelectric α‐In₂Se₃. The electronic logic bit can be represented and stored with different orientations of electric dipoles in the top‐gate ferroelectric. The 2D FeFET can be randomly rewritten over more than 10⁵ cycles without losing the nonvolatility. The approach demonstrates a prototype of rewritable nonvolatile memory with ferroelectricity in van der Waals 2D materials.     

Laterally Heterogeneous 2D Layered Materials as an Artificial Light‐Harvesting Proton Pump

Heterogeneous structures in nacre‐mimetic 2D layered materials generate novel transport phenomena in angstrom range, and thus provide new possibilities for innovative applications for sustainable energy, a clean environment, and human healthcare. In the two orthogonal transport directions, either vertical or horizontal, heterostructures in horizontal direction have never been reported before. Here, a 2D‐material‐based laterally heterogeneous membrane is fabricated via an unconventional dual‐flow filtration method. Negatively and positively charged graphene oxide multilayers are laterally patterned and interconnected in a planar configuration. Upon visible light illumination on the bipolar nanofluidic heterojunction, protons are able to move uphill against their concentration gradient, functioning as a light‐harvesting proton pump. A maximum proton concentration gradient of about 5.4 pH units mm^?2 membrane area can be established at a transport rate up to 14.8 mol h^?1 m^?2. The transport mechanism can be understood as a light‐triggered asymmetric polarization in surface potential and the consequent change in proton capacity in separate parts. The implementation of photonic–ionic conversion with abiotic materials provides a full‐solid‐state solution for bionic vision and artificial photosynthesis. There is plenty of room to expect the laterally heterogeneous membranes for new functions and better performance in the abundant family of liquid processable colloidal 2D materials.     

Inkjet Printed Large‐Area Flexible Few‐Layer Graphene Thermoelectrics

Graphene‐based organic nanocomposites have ascended as promising candidates for thermoelectric energy conversion. In order to adopt existing scalable printing methods for developing thermostable graphene‐based thermoelectric devices, optimization of both the material ink and the thermoelectric properties of the resulting films are required. Here, inkjet‐printed large‐area flexible graphene thin films with outstanding thermoelectric properties are reported. The thermal and electronic transport properties of the films reveal the so‐called phonon‐glass electron‐crystal character (i.e., electrical transport behavior akin to that of few‐layer graphene flakes with quenched thermal transport arising from the disordered nanoporous structure). As a result, the all‐graphene films show a room‐temperature thermoelectric power factor of 18.7 µW m^?1 K^?2, representing over a threefold improvement to previous solution‐processed all‐graphene structures. The demonstration of inkjet‐printed thermoelectric devices underscores the potential for future flexible, scalable, and low‐cost thermoelectric applications, such as harvesting energy from body heat in wearable applications.     

Large‐Area Synthesis of Continuous and Uniform MoS2 Monolayer Films on Graphene

Heterostructures composed of multiple layers of different atomically thin materials are of interest due to their unique properties and potential for new device functionality. MoS₂‐graphene heterostructures have shown promise as photodetectors and vertical tunnel transistors. However, progress is limited by the typically micrometer‐scale devices and by the multiple alignments required for fabrication when utilizing mechanically exfoliated material. Here, the synthesis of large‐area, continuous, and uniform MoS₂ monolayers directly on graphene by chemical vapor deposition is reported, resulting in heterostructure samples on the centimeter scale with the possibility for even larger lateral dimensions. Atomic force microscopy, photoluminescence, X‐ray photoelectron, and Raman spectroscopies demonstrate uniform single‐layer growth of stoichiometric MoS₂. The ability to reproducibly generate large‐area heterostructures is highly advantageous for both fundamental investigations and technological applications.     

Inter-Flake Quantum Transport of Electrons and Holes in Inkjet-Printed Graphene Devices

2D materials have unique structural and electronic properties with potential for transformative device applications. However, such devices are usually bespoke structures made by sequential deposition of exfoliated 2D layers. There is a need for scalable manufacturing techniques capable of producing high-quality large-area devices comprising multiple 2D materials. Additive manufacturing with inks containing 2D material flakes is a promising solution. Inkjet-printed devices incorporating 2D materials have been demonstrated, however there is a need for greater understanding of quantum transport phenomena as well as their structural properties. Experimental and theoretical studies of inkjet-printed graphene structures are presented. Detailed electrical and structural characterization is reported and explained by comparison with transport modeling that include inter-flake quantum tunneling transport and percolation dynamics. The results reveal that the electrical properties are strongly influenced by the flakes packing fraction and by complex meandering electron trajectories, which traverse several printed layers. Controlling these trajectories is essential for printing high-quality devices that exploit the properties of 2D materials. Inkjet-printed graphene is used to make a field effect transistor and Ohmic contacts on an InSe phototransistor. This is the first time that inkjet-printed graphene has successfully replaced single layer graphene as a contact material for 2D metal chalcogenides.     

Metal-Organic Framework Thin Films Grown on Functionalized Graphene as Solid-State Ion-Gated FETs

The unique properties of 2D-materials like graphene are exploited in various electronic devices. In sensor applications, graphene shows a very high sensitivity, but only a low specificity. This shortcoming can be mastered by using heterostructures, where graphene is combined with materials exhibiting high analyte selectivities. Herein, this study demonstrates the precise deposition of nanoporous metal-organic frameworks (MOFs) on graphene, yielding bilayers with excellent specificity while the sensitivity remains large. The key for the successful layer-by-layer deposition of the MOF films (SURMOFs) is the use of planar polyaromatic anchors. Then, the MOF pores are loaded with ionic liquid (IL). For functioning sensor devices, the IL@MOF films are grown on graphene field-effect transistors (GFETs). Adding a top-gate electrode yields an ion-gated GFET. Analysis of the transistor characteristics reveals a clear Dirac point at low gate voltages, good on-off ratios, and decent charge mobilities and densities in the graphene channel. The GFET-sensor reveals a strong and selective response. Compared to other ion-gated-FET devices, the IL@MOF material is relatively hard, allowing the manufacturing of ultrathin devices. The new MOF-anchoring strategy offers a novel approach generally applicable for the functionalization of 2D-materials, where MOF/2D-material hetero-bilayers carry a huge potential for a wide variety of applications.     

Polar heterostructure for multifunction devices: theoretical studies

We examine the potential of devices based on heterostructures made from highly polar materials and semiconductors. Our calculations show that such functional devices have superior sensor properties and transistor properties. The basis device examined is based on the use of a thin oxide with high piezoelectric coefficients or pyroelectric coefficients under the gate region. Channel charge and current are controlled by gate voltage, temperature, or stress. We examine the performance of three classes of heterostructures that form the basis of important semiconductor technologies: 1) Si-SiO/sub 2/-BaTiO/sub 3/ heterostructure junctions that would be an important breakthrough for silicon sensor technology; 2) GaN-AlN-BaTiO/sub 3/ heterostructure junctions that would be important especially in high temperature sensor application; and 3) GaAs-AlGaAs-BaTiO/sub 3/ heterostructure field effect transistors. The calculations show that with a very thin polar material layer we can have a highly sensitive sensor and transistor. For optimum performance, the polar material (piezoelectric or pyroelectric) layer thickness should be /spl sim/30 /spl Aring/.     

Single‐Crystal Hybrid Perovskite Platelets on Graphene: A Mixed‐Dimensional Van Der Waals Heterostructure with Strong Interface Coupling

Van der Waals (vdW) heterostructures open up excellent prospects in electronic and optoelectronic applications. In this work, mixed‐dimensional metal‐halide perovskite/graphene heterostructures are prepared through selective growth of CH₃NH₃PbBr₃ platelets on patterned single‐layer graphene using chemical vapor deposition. Preferred growth of single‐crystal CH₃NH₃PbBr₃ platelets on graphene surfaces is achieved, which is accompanied by significant photoluminescence quenching. Raman spectra reveal that perovskite platelets cause p‐type doping in the graphene layer. A significant Fermi level decrease of 272 meV in graphene is estimated, which corresponds to a high doping density of 7.5 × 10¹² cm^?2. Surface potentials measured by Kelvin probe force microscopy indicate a negatively charged perovskite surface under illumination, which is consistent with the upward band bending deduced from conducting atomic force microscopy measurements. Moreover, a field‐effect phototransistor is fabricated using the perovskite/graphene heterostructure channel, and the increased Dirac voltage under illumination confirms an enhanced p‐type character in graphene. These findings enrich the understanding of strong interface coupling in such mixed‐dimensional vdW heterostructures and pave the way toward novel perovskite‐based optoelectronic devices.     

Dirac Cone Spin Polarization of Graphene by Magnetic Insulator Proximity Effect Probed with Outermost Surface Spin Spectroscopy

The effects of the proximity contact with magnetic insulator on the spin‐dependent electronic structure of graphene are explored for the heterostructure of single‐layer graphene (SLG) and yttrium iron garnet Y₃Fe₅O₁₂ (YIG) by means of outermost surface spin spectroscopy using a spin‐polarized metastable He atom beam. In the SLG/YIG heterostructure, the Dirac cone electrons of graphene are found to be negatively spin polarized in parallel to the minority spins of YIG with a large polarization degree, without giving rise to significant changes in the π band structure. Theoretical calculations reveal the electrostatic interfacial interactions providing a strong physical adhesion and the indirect exchange interaction causing the spin polarization of SLG at the interface with YIG. The Hall device of the SLG/YIG heterostructure exhibits a nonlinear Hall resistance attributable to the anomalous Hall effect, implying the extrinsic spin–orbit interactions as another manifestation of the proximity effect.     

Cover Picture: An Organic Light‐Emitting Diode with Field‐Effect Electron Transport (Adv. Funct. Mater. 1/2008)

The cover shows an organic light‐emitting diode with remote metallic cathode, reported by Sarah Schols and co‐workers on p. 136. The metallic cathode is displaced from the light‐emission zone by one to several micrometers. The injected electrons accumulate at an organic heterojunction and are transported to the light‐emission zone by field‐effect. The achieved charge‐carrier mobility and in combination with reduced optical absorption losses because of the remoteness of the cathode may lead to applications as waveguide OLEDs and possibly a laser structure. (The result was obtained in the EU‐funded project “OLAS” IST‐ FP6‐015034.) We describe an organic light‐emitting diode (OLED) using field‐effect to transport electrons. The device is a hybrid between a diode and a field‐effect transistor. Compared to conventional OLEDs, the metallic cathode is displaced by one to several micrometers from the light‐emitting zone. This micrometer‐sized distance can be bridged by electrons with enhanced field‐effect mobility. The device is fabricated using poly(triarylamine) (PTAA) as the hole‐transport material, tris(8‐hydroxyquinoline) aluminum (Alq₃) doped with 4‐(dicyanomethylene)‐2‐methyl‐6‐(julolindin‐4‐yl‐vinyl)‐4H‐pyran (DCM₂) as the active light‐emitting layer, and N,N′‐ditridecylperylene‐3,4,9,10‐tetracarboxylic diimide (PTCDI‐C₁₃H₂₇), as the electron‐transport material. The obtained external quantum efficiencies are as high as for conventional OLEDs comprising the same materials. The quantum efficiencies of the new devices are remarkably independent of the current, up to current densities of more than 10 A cm^–2. In addition, the absence of a metallic cathode covering the light‐emission zone permits top‐emission and could reduce optical absorption losses in waveguide structures. These properties may be useful in the future for the fabrication of solid‐state high‐brightness organic light sources.     

Field-Effect Chiral Anomaly Devices with Dirac Semimetal

Charge-based field-effect transistors (FETs) greatly suffer from unavoidable carrier scattering and heat dissipation. Analogous to valley degree of freedom in semiconductors, chiral anomaly current in Weyl/Dirac semimetals is theoretically predicted to be nearly nondissipative over long distances, but still lacks experimental ways to efficiently control its transport. Here, field-effect chirality devices are demonstrated with Dirac semimetal PtSe₂, in which its Fermi level is close to the Dirac point in the conduction band owing to intrinsic defects. The chiral anomaly is further corroborated by the planar Hall effect and nonlocal valley transport measurement, which can also be effectively modulated by external fields, showing robust nonlocal valley transport with micrometer diffusion length. Similar to charge-based FETs, the chiral conductivity in PtSe₂ devices can be modulated by electrostatic gating with an ON/OFF ratio of more than 10³. Basic logic functions in the devices are also demonstrated with electric and magnetic fields as input signals.     

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.     

Oxygen‐Free Highly Conductive Graphene Papers

Graphene papers have a potential to overcome the gap from nanoscale graphene to real macroscale applications of graphene. A unique process for preparation of highly conductive graphene thin paper by means of Ar⁺ ion irradiation of graphene oxide (GO) papers, with carbon/oxygen ratio reduced to 100:1, is presented. The composition of graphene paper in terms of carbon/oxygen ratio and in terms of types of individual oxygen‐containing groups is monitored throughout the process. Angle‐resolved high resolution X‐ray photoelectron spectroscopy helps to investigate the depth profile of carbon and oxygen within reduced GO paper. C/O ratios over 100 on the surface and 40 in bulk material are observed. In order to bring insight to the processes of oxygen removal from GO paper by low energy Ar⁺ ion bombardment, the gases released during the irradiation are analyzed by mass spectroscopy. It is proven that Ar⁺ ion beam can be applied as a technique for fabrication of highly reduced graphene papers with high conductivities. Such highly conductive graphene papers have great potential to be used in application for construction of microelectronic and sensor devices.     

Graphene Heterostructure Integrated Optical Fiber Bragg Grating for Light Motion Tracking and Ultrabroadband Photodetection from 400 nm to 10.768 µm

Integrated photonics and optoelectronics devices based on graphene and related 2D materials are at the core of the future industrial revolution, facilitating compact and flexible nanophotonic devices. Tracking and detecting the motion of broadband light in millimeter to nanometer scale is an unfold science which has not been fully explored. In this work, tracking and detecting the motion of light (millimeter precision) is first demonstrated by integrating graphene with an optical fiber Bragg grating device (graphene‐FBG). When the incident light moves toward and away from the graphene‐FBG device, the Bragg wavelength red‐shifts and blue‐shifts, indicating its light motion tracking ability. Such light tracking capability can be further extended to an ultrabroad wavelength range as all‐optical photodetectors show the robust response from 400 nm to 10.768 µm with a linear optical response. Interestingly, it is found that graphene‐Bi₂Te₃ heterostructure on FBG shows 87% higher photoresponse than graphene‐FBG at both visible and telecom wavelengths, due to stronger phonon‐electron coupling and photo‐thermal conversion in the heterostructure. The device also shows superior stability even after 100 d. This work may open up amazing integrated nanophotonics applications such as astrophysics, optical communication, optical computing, optical logic gating, spectroscopy, and laser biology.     

Low‐Noise Multispectral Photodetectors Made from All Solution‐Processed Inorganic Semiconductors

Infrared, visible, and multispectral photodetectors are important components for sensing, security and electronics applications. Current fabrication of these devices is based on inorganic materials grown by epitaxial techniques which are not compatible with low‐cost large‐scale processing. Here, air‐stable multispectral solution‐processed inorganic double heterostructure photodetectors, using PbS quantum dots (QDs) as the photoactive layer, colloidal ZnO nanoparticles as the electron transport/hole blocking layer (ETL/HBL), and solution‐derived NiO as the hole transport/electron blocking layer (HTL/EBL) are reported. The resulting device has low dark current density of 20 nA cm^‐2 with a noise equivalent power (NEP) on the order of tens of picowatts across the detection spectra and a specific detectivity (D*) value of 1.2 × 10¹² cm Hz^1/2 W^‐1. These parameters are comparable to commercially available Si, Ge, and InGaAs photodetectors. The devices have a linear dynamic range (LDR) over 65 dB and a bandwidth over 35 kHz, which are sufficient for imaging applications. Finally, these solution‐processed inorganic devices have a long storage lifetime in air, even without encapsulation.     

Thermal Transport in 2D Semiconductors—Considerations for Device Applications

The discovery of graphene has stimulated the search for and investigations into other 2D materials because of the rich physics and unusual properties exhibited by many of these layered materials. Transition metal dichalcogenides (TMDs), black phosphorus, and SnSe among many others, have emerged to show highly tunable physical and chemical properties that can be exploited in a whole host of promising applications. Alongside the novel electronic and optical properties of such 2D semiconductors, their thermal transport properties have also attracted substantial attention. Here, a comprehensive review of the unique thermal transport properties of various emerging 2D semiconductors is provided, including TMDs, black‐ and blue‐phosphorene among others, and the different mechanisms underlying their thermal conductivity characteristics. The focus is placed on the phonon‐related phenomena and issues encountered in various applications based on 2D semiconductor materials and their heterostructures, including thermoelectric power generation and electron–phonon coupling effect in photoelectric and thermal transistor devices. A thorough understanding of phonon transport physics in 2D semiconductor materials to inform thermal management of next‐generation nanoelectronic devices is comprehensively presented along with strategies for controlling heat energy transport and conversion.     

Functionalized Graphene Superlattice as a Single‐Sheet Solar Cell

In‐plane heterostructure engineering provides unique opportunities to control device properties. Here, a single‐sheet solar cell made of a graphene sheet functionalized into 1D channels is explored. Compared to vertical heterostructure architectures based on 2D materials, the single‐sheet solar cell shows potential for improved robustness against defects, enhancement of polaron dissociation, extra freedom for functionalization, and coverage of the entire solar spectrum. The partition width, device length, and functionalizations can be tuned independently to optimize the key optoelectronic properties for photovoltaic performance.     

Van der Waals Heterostructure Devices with Dynamically Controlled Conduction Polarity and Multifunctionality

Controlling the conduction behavior of 2D materials is an important prerequisite to achieve their electronic and optoelectronic applications. However, most of the reported approaches are aware of the shortcomings of inflexibility and complexity, which limits the possibility of multifunctional integration. Here, taking advantage of van der Waals heterostructure engineering, a simple method to achieve a dynamically controlled binary channel in a semivertical MoTe₂/MoS₂ field effect transistor is proposed. It is enabled by the high switchability between tunneling and thermal transports through simply changing the sign of voltage bias. In addition, the proposed system allows for multifunctional integration of transistor with on/off ratio >10⁷ and diode with rectification ratio >10⁶. Moreover, the devices show screen capability to negative photoresponse effect that is widely observed in ambipolar materials, hence improving the photodetection reliability and sensitivity. This study broadens the functionalities of van der Waals heterostructures and opens up more possibilities to realize multifunctional devices.