Two-dimensional (2D) semiconductors, such as ultrathin layers of transition metal dichalcogenides (TMDs), offer a unique combination of electronic, optical and mechanical properties, and hold ...potential to enable a host of new device applications spanning from flexible/wearable (opto)electronics to energy-harvesting and sensing technologies. A critical requirement for developing practical and reliable electronic devices based on semiconducting TMDs consists in achieving a full control over their charge-carrier polarity and doping. Inconveniently, such a challenging task cannot be accomplished by means of well-established doping techniques (
e.g.
ion implantation and diffusion), which unavoidably damage the 2D crystals resulting in degraded device performances. Nowadays, a number of alternatives are being investigated, including various (supra)molecular chemistry approaches relying on the combination of 2D semiconductors with electroactive donor/acceptor molecules. As yet, a large variety of molecular systems have been utilized for functionalizing 2D TMDs
via
both covalent and non-covalent interactions. Such research endeavours enabled not only the tuning of the charge-carrier doping but also the engineering of the optical, electronic, magnetic, thermal and sensing properties of semiconducting TMDs for specific device applications. Here, we will review the most enlightening recent advancements in experimental (supra)molecular chemistry methods for tailoring the properties of atomically-thin TMDs - in the form of substrate-supported or solution-dispersed nanosheets - and we will discuss the opportunities and the challenges towards the realization of novel hybrid materials and devices based on 2D semiconductors and molecular systems.
A variety of molecular chemistry approaches are currently investigated for tailoring the physico-chemical properties of ultrathin transition metal dichalcogenides towards novel hybrid multifunctional materials and devices.
Stimuli-responsive hybrid van der Waals heterostructures (vdWHs), composed of organic molecular switches superimposed on inorganic 2D materials (2DMs), can combine the outstanding physical properties ...of the latter components with the virtually infinite variety of tunable functionality of molecules, thereby offering an efficient protocol for the development of high-performance multifunctional materials and devices. The use of light as a remote control to modulate the properties of semiconducting 2DMs when interfaced with photochromic molecules suffers from both the limitation associated with the persistent photoconductivity characterizing the 2DMs and the finite thermal stability of the photochromic molecule in its different states. Here, we have devised a universal approach toward the fabrication of optically switchable electronic devices comprising a few nanometers thick azobenzene (AZO) layer physisorbed on 2D semiconductors supported on a trap-free polymer dielectric. The joint effect of the improved 2D/dielectric interface, the molecule’s light-modulated dipolar doping, and the high thermal stability of cis-AZO offers the highest control over the reversible and efficient charge carrier tuning in 2D semiconductors with a preserved high performance in 2D field-effect transistors, as quantified in terms of carrier mobility and I on/I off ratio. The device has the potential to operate as an optical memory with four current levels and long retention time (>15 h). Furthermore, by using a CMOS-compatible micropatterning process, the photoswitchable resistor–diode transition has been achieved on hybrid lateral heterojunction devices. Our approach is of general applicability toward the generation of high-performance hybrid vdWHs for the emergence of functional and responsive devices.
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Femtosecond transient absorption spectroscopy and microscopy were employed to study exciton dynamics in suspended and Si3N4 substrate-supported monolayer and few-layer MoS2 2D crystals. Exciton ...dynamics for the monolayer and few-layer structures were found to be remarkably different from those of thick crystals when probed at energies near that of the lowest energy direct exciton (A exciton). The intraband relaxation rate was enhanced by more than 40 fold in the monolayer in comparison to that observed in the thick crystals, which we attributed to defect assisted scattering. Faster electron–hole recombination was found in monolayer and few-layer structures due to quantum confinement effects that lead to an indirect–direct band gap crossover. Nonradiative rather than radiative relaxation pathways dominate the dynamics in the monolayer and few-layer MoS2. Fast trapping of excitons by surface trap states was observed in monolayer and few-layer structures, pointing to the importance of controlling surface properties in atomically thin crystals such as MoS2 along with controlling their dimensions.
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The pervasiveness of information technologies is generating an impressive amount of data, which need to be accessed very quickly. Nonvolatile memories (NVMs) are making inroads into high‐capacity ...storage to replace hard disk drives, fuelling the expansion of the global storage memory market. As silicon‐based flash memories are approaching their fundamental limit, vertical stacking of multiple memory cell layers, innovative device concepts, and novel materials are being investigated. In this context, emerging 2D materials, such as graphene, transition metal dichalcogenides, and black phosphorous, offer a host of physical and chemical properties, which could both improve existing memory technologies and enable the next generation of low‐cost, flexible, and wearable storage devices. Herein, an overview of graphene and related 2D materials (GRMs) in different types of NVM cells is provided, including resistive random‐access, flash, magnetic and phase‐change memories. The physical and chemical mechanisms underlying the switching of GRM‐based memory devices studied in the last decade are discussed. Although at this stage most of the proof‐of‐concept devices investigated do not compete with state‐of‐the‐art devices, a number of promising technological advancements have emerged. Here, the most relevant material properties and device structures are analyzed, emphasizing opportunities and challenges toward the realization of practical NVM devices.
The outstanding properties of graphene and related 2D materials (GRMs) make them unique components for nonvolatile memories (NVMs) with enhanced characteristics to enable the next generation of low‐cost, flexible, and wearable information‐storage devices. An overview of different GRM‐based NVM cells, including resistive random‐access, flash, magnetic, and phase‐change memories, is presented, emphasizing both opportunities and challenges toward the realization of practical NVM devices by exploiting the unique properties of GRMs.
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Atomically thin molybdenum disulfide (MoS2) offers potential for advanced devices and an alternative to graphene due to its unique electronic and optical properties. The temperature-dependent Raman ...spectra of exfoliated, monolayer MoS2 in the range of 100–320 K are reported and analyzed. The linear temperature coefficients of the in-plane E 2g 1 and the out-of-plane A 1g modes for both suspended and substrate-supported monolayer MoS2 are measured. These data, when combined with the first-order coefficients from laser power-dependent studies, enable the thermal conductivity to be extracted. The resulting thermal conductivity κ = (34.5 ± 4) W/mK at room temperature agrees well with the first-principles lattice dynamics simulations. However, this value is significantly lower than that of graphene. The results from this work provide important input for the design of MoS2-based devices where thermal management is critical.
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Conventional floating-gate (FG) transistors (made with Si/poly-Si) that form the building blocks of the widely employed nonvolatile flash memory technology face severe scaling challenges beyond the ...12-nm node. In this paper, for the first time, a comprehensive evaluation of the FG transistor made from emerging nanocrystals in the form of 2-dimensional (2D) transition metal dichalcogenides (TMDs) and multilayer graphene (MLG) is presented. It is shown that TMD based 2D channel materials have excellent gate length scaling potential due to their atomic scale thicknesses. On the other hand, employing MLG as FG greatly reduces cell-to-cell interference and alleviates reliability concerns. Moreover, it is also revealed that TMD/MLG heterostructures enable new mechanism for improving charge retention, thereby allowing the effective oxide thickness of gate dielectrics to be scaled to a few nanometers. Thus, this work indicates that judiciously selected 2D-nanocrystals can significantly extend the lifetime of the FG-based memory cell.
Molecular switches enable the fabrication of multifunctional devices in which an electrical output can be modulated by external stimuli. The working mechanism of these devices is often hard to prove, ...since the molecular switching events are only indirectly confirmed through electrical characterization, without real-space visualization. Here, we show how photochromic molecules self-assembled on graphene and MoS
generate atomically precise superlattices in which a light-induced structural reorganization enables precise control over local charge carrier density in high-performance devices. By combining different experimental and theoretical approaches, we achieve exquisite control over events taking place from the molecular level to the device scale. Unique device functionalities are demonstrated, including the use of spatially confined light irradiation to define reversible lateral heterojunctions between areas possessing different doping levels. Molecular assembly and light-induced doping are analogous for graphene and MoS
, demonstrating the generality of our approach to optically manipulate the electrical output of multi-responsive hybrid devices.
The spatially precise integration of arrays of micropatterned two-dimensional (2D) crystals onto three-dimensionally structured Si/SiO2 substrates represents an attractive, low-cost system-on-chip ...strategy toward the realization of extended functions in silicon microelectronics. However, the reliable integration of such atomically thin arrays on planar patterned surfaces has proven challenging due to their poor adhesion to underlying substrates, as ruled by weak van der Waals interactions. Here, we report on an integration method utilizing the flexibility of the atomically thin crystals and their physical subsidence in liquids, which enables the reliable fabrication of the micropatterned 2D materials/Si arrays. Our photodiode devices display peak sensitivity as high as 0.35 A/W and external quantum efficiency (EQE) of ∼90%. The nano-subsidence technique represents a viable path to on-chip integration of 2D crystals onto silicon for advanced microelectronics.
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Memory cells are an important building block of digital electronics. We combine here the unique electronic properties of semiconducting monolayer MoS2 with the high conductivity of graphene to build ...a 2D heterostructure capable of information storage. MoS2 acts as a channel in an intimate contact with graphene electrodes in a field-effect transistor geometry. Our prototypical all-2D transistor is further integrated with a multilayer graphene charge trapping layer into a device that can be operated as a nonvolatile memory cell. Because of its band gap and 2D nature, monolayer MoS2 is highly sensitive to the presence of charges in the charge trapping layer, resulting in a factor of 104 difference between memory program and erase states. The two-dimensional nature of both the contact and the channel can be harnessed for the fabrication of flexible nanoelectronic devices with large-scale integration.
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