The development of silicon semiconductor technology has produced breakthroughs in electronics—from the microprocessor in the late 1960s to early 1970s, to automation, computers and smartphones—by downscaling the physical size of devices and wires to the nanometre regime. Now, graphene and related two-dimensional (2D) materials offer prospects of unprecedented advances in device performance at the atomic limit, and a synergistic combination of 2D materials with silicon chips promises a heterogeneous platform to deliver massively enhanced potential based on silicon technology. Integration is achieved via three-dimensional monolithic construction of multifunctional high-rise 2D silicon chips, enabling enhanced performance by exploiting the vertical direction and the functional diversification of the silicon platform for applications in opto-electronics and sensing. Here we review the opportunities, progress and challenges of integrating atomically thin materials with silicon-based nanosystems, and also consider the prospects for computational and non-computational applications. Progress in integrating atomically thin two-dimensional materials with silicon-based technology is reviewed, together with the associated opportunities and challenges, and a roadmap for future applications is presented.

Graphene and two-dimensional materials for silicon technology.

Two-dimensional (2D) semiconductors have attracted tremendous interest as atomically thin channels that could facilitate continued transistor scaling. However, despite many proof-of-concept demonstrations, the full potential of 2D transistors has yet to be determined. To this end, the fundamental merits and technological limits of 2D transistors need a critical assessment and objective projection. Here we review the promise and current status of 2D transistors, and emphasize that widely used device parameters (such as carrier mobility and contact resistance) could be frequently misestimated or misinterpreted, and may not be the most reliable performance metrics for benchmarking 2D transistors. We suggest that the saturation or on-state current density, especially in the short-channel limit, could provide a more reliable measure for assessing the potential of diverse 2D semiconductors, and should be applied for cross-checking different studies, especially when milestone performance metrics are claimed. We also summarize the key technical challenges in optimizing the channels, contacts, dielectrics and substrates and outline potential pathways to push the performance limit of 2D transistors. We conclude with an overview of the critical technical targets, the key technological obstacles to the 'lab-to-fab' transition and the potential opportunities arising from the use of these atomically thin semiconductors.

Promises and prospects of two-dimensional transistors

© 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown.

Production and processing of graphene and related materials

Gas sensors based on a chemiresistive metal oxide semiconductor are widely used including nitrogen dioxide (NO 2 ) at a moderate temperature. In this work efforts are taken to fabricate NO 2 gas sensor using thin films of tungsten oxide (WO 3 ) grown directly on to a soda-lime glass substrate without assistance of any seed layer by a simple and a facile hydrothermal technique. As per our knowledge, the deposition of nanostructured WO 3 thin films without assistance of any seed layer on the glass substrate was rarely reported. The WO 3 thin film samples were synthesized at various deposition times ranging from 3 h to 7 h and were characterized by X-ray diffraction, Raman spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, UV–vis spectroscopy and Brunauer-Emmett-Teller techniques. The surface morphological and structural characterization showed the two dimensional (2D) nanoplate-like structure of as synthesized WO 3 thin films with plate thickness ranging from 90 to 150 nm and had an orthorhombic structure, respectively. Moreover, the 2D nanoplates of WO 3 exhibited a gas response ∼10 for 5 ppm for toxic NO 2 gas at relatively low operating temperature. The new synthesis route and sensing behavior of as synthesized WO 3 nanoplates revealed a promising candidate for the fabrication of the cost effective gas sensors.

Sensitive and selective NO2 gas sensor based on WO3 nanoplates

Two-dimensional semiconductors (2DSCs) have attracted considerable attention as atomically thin channel materials for field-effect transistors. Each layer in 2DSCs consists of a single- or few-atom-thick, covalently bonded lattice, in which all carriers are confined in their atomically thin channel with superior gate controllability and greatly suppressed OFF-state current, in contrast to typical bulk semiconductors plagued by short channel effects and heat generation from static power. Additionally, 2DSCs are free of surface dangling bonds that plague traditional semiconductors, and hence exhibit excellent electronic properties at the limit of single atom thickness. Therefore, 2DSCs can offer significant potential for the ultimate transistor scaling to single atomic body thickness. Earlier studies of graphene transistors have been limited by the zero bandgap and low ON–OFF ratio of graphene, and transition metal dichalcogenide (TMDC) devices are typically plagued by insufficient carrier mobility. To this end, considerable efforts have been devoted towards searching for new 2DSCs with optimum electronic properties. Within a relatively short period of time, a large number of 2DSCs have been demonstrated to exhibit unprecedented characteristics or unique functionalities. Here we review the recent efforts and progress in exploring novel 2DSCs beyond graphene and TMDCs for ultra-thin body transistors, discussing the merits, limits and prospects of each material.

Two-dimensional transistors beyond graphene and TMDCs

Current methods of chemical vapour deposition (CVD) of graphene on copper are complicated by multiple processing steps and by high temperatures required in both preparing the copper and inducing subsequent film growth. Here we demonstrate a plasma-enhanced CVD chemistry that enables the entire process to take place in a single step, at reduced temperatures (o420C), and in a matter of minutes. Growth on copper foils is found to nucleate from arrays of well-aligned domains, and the ensuing films possess sub-nanometre smoothness, excellent crystalline quality, low strain, few defects and roomtemperature electrical mobility up to (6.0±1.0) � 10 4 cm 2 V � 1 s � 1 , better than that of large,

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Single-step deposition of high-mobility graphene at reduced temperatures

We studied wave function dissipation (WFD) in field emission resonance (FER) by performing scanning tunneling microscopy on the highly oriented pyrolytic graphite (HOPG) and Ag(111) surfaces under two conditions: (1) the same current and FER number; (2) the same tip structure but different currents. Under the first condition, we observed that the decay rate corresponding to the WFD exhibited a larger variation on the HOPG surface than it did on the Ag(111) surface. Under the second condition, the decay rate was nearly independent of the FER electric field for the Ag(111) surface; by contrast, it was linearly proportional to the FER electric field for the HOPG surface. These remarkable differences can be attributed to the factors that the tip-induced attractive deformation caused by the electrostatic force was considerably more prominent on the HOPG surface than on the Ag(111) surface and that the deformed HOPG top layer had a unique electronic structure similar to that of single-layer graphene.

Probing tip-induced attractive deformation of graphite surfaces through wave function dissipation in field emission resonance

The apex structure of a scanning tunneling microscope (STM) tip consists of a base with radius of tens of nanometers and protrusion with atomic-scale sharpness. We characterized the tip base radius and sharpness on the basis of field emission resonance (FER) energies. We derived two quantities from the first- through sixth-order FER energies, which were related to tip sharpness and base radius. The base radius can remain unchanged while the sharpness varied, and the tips can have identical sharpness but different base radii. The base radius can significantly affect the peak intensities of FER, which corresponds to the mean lifetime of FER electrons, on a Ag(100) surface but not on those of FER on a Ag(111) surface. This difference results from the surface dipole layer and quantum trapping effect (QTE) on the Ag(100) surface which are greater than those on the Ag(111) surface.

Characterization of apex structures of scanning tunneling microscope tips with field emission resonance energies

In this study, we discovered that the energy gap above the vacuum level in the projected bulk band structure of Ag(100) prevents electrons in the first-order field emission resonance (FER) from inducing the surface plasmons. This mechanism allows light emission from FER to reveal characteristics of triplet states and Auger-type excitation resulting from two-electron tunneling in FER. According to optical spectra, surface plasmons can be induced by electrons in the zeroth-order FER. However, corresponding radiative decay can also trigger Auger-type excitation, whose energy state is influenced by the sharpness-dependent image potential acting on the scanning tunneling microscope tip.

W.-Y. Chan

Papers

Single-step deposition of high-mobility graphene at reduced temperatures

Probing tip-induced attractive deformation of graphite surfaces through wave function dissipation in field emission resonance

Characterization of apex structures of scanning tunneling microscope tips with field emission resonance energies

Triplet State and Auger-Type Excitation Originating from Two-Electron Tunneling in Field Emission Resonance on Ag(100)