Thickness Trends of Electron and Hole Conduction and Contact Carrier Injection in Surface Charge Transfer Doped 2D Field Effect Transistors.

One of the main limiting factors in the performance of devices based on two-dimensional (2D) materials is Fermi level pinning at the contacts, which creates Schottky barriers (SBs) that increase contact resistance and, for most transition metal dichalcogenides (TMDs), limit hole conduction. A promising method to mitigate these problems is surface charge transfer doping (SCTD), which places fixed charge at the surface of the material and thins the SBs by locally shifting the energy bands. We use a mild O2 plasma to convert the top few layers of a given TMD into a substoichiometric oxide that serves as a p-type SCTD layer. A comprehensive experimental study, backed by TCAD simulations, involving MoS2, MoSe2, MoTe2, WS2, and WSe2 flakes of various thicknesses exposed to different plasma times is used to investigate the underlying mechanisms responsible for SCTD. The surface charge at the top of the channel and the gate-modulated surface potential at the bottom are found to have competing effects on the channel potential, which results in a decrease in the doping-induced threshold shift and an increase in minimum OFF state current with increasing thickness. Additionally, an undoped channel region is shown to mitigate carrier injection issues in sufficiently thin flakes. Notably, the band movements underlying the SCTD effects are independent of the particular semiconductor material, SCTD strategy, and doping polarity. Consequently, our findings provide critical insights for the design of high-performance transistors for a wide range of materials and SCTD mechanisms including TMD devices with strong hole conduction.

Carbon doping of WS2 monolayers: Bandgap reduction and p-type doping transport.

Chemical doping constitutes an effective route to alter the electronic, chemical, and optical properties of two-dimensional transition metal dichalcogenides (2D-TMDs). We used a plasma-assisted method to introduce carbon-hydrogen (CH) units into WS2 monolayers. We found CH-groups to be the most stable dopant to introduce carbon into WS2, which led to a reduction of the optical bandgap from 1.98 to 1.83 eV, as revealed by photoluminescence spectroscopy. Aberration corrected high-resolution scanning transmission electron microscopy (AC-HRSTEM) observations in conjunction with first-principle calculations confirm that CH-groups incorporate into S vacancies within WS2. According to our electronic transport measurements, undoped WS2 exhibits a unipolar n-type conduction. Nevertheless, the CH-WS2 monolayers show the emergence of a p-branch and gradually become entirely p-type, as the carbon doping level increases. Therefore, CH-groups embedded into the WS2 lattice tailor its electronic and optical characteristics. This route could be used to dope other 2D-TMDs for more efficient electronic devices.

Craniobot: A computer numerical controlled robot for cranial microsurgeries.

Over the last few decades, a plethora of tools has been developed for neuroscientists to interface with the brain. Implementing these tools requires precisely removing sections of the skull to access the brain. These delicate cranial microsurgical procedures need to be performed on the sub-millimeter thick bone without damaging the underlying tissue and therefore, require significant training. Automating some of these procedures would not only enable more precise microsurgical operations, but also facilitate widespread use of advanced neurotechnologies. Here, we introduce the "Craniobot", a cranial microsurgery platform that combines automated skull surface profiling with a computer numerical controlled (CNC) milling machine to perform a variety of cranial microsurgical procedures on mice. The Craniobot utilizes a low-force contact sensor to profile the skull surface and uses this information to perform precise milling operations within minutes. We have used the Craniobot to perform intact skull thinning and open small to large craniotomies over the dorsal cortex.

Defect-Controlled Nucleation and Orientation of WSe2 on hBN: A Route to Single-Crystal Epitaxial Monolayers.

A defect-controlled approach for the nucleation and epitaxial growth of WSe2 on hBN is demonstrated. The WSe2 domains exhibit a preferred orientation of over 95%, leading to a reduced density of inversion domain boundaries (IDBs) upon coalescence. First-principles calculations and experimental studies as a function of growth conditions and substrate pretreatment confirm that WSe2 nucleation density and orientation are controlled by the hBN surface defect density rather than thermodynamic factors. Detailed transmission electron microscopy analysis provides support for the role of single-atom vacancies on the hBN surface that trap W atoms and break surface symmetry leading to a reduced formation energy for one orientation of WSe2 domains. Through careful control of nucleation and extended lateral growth time, fully coalesced WSe2 monolayer films on hBN were achieved. Low-temperature photoluminescence (PL) measurements and transport measurements of back-gated field-effect transistor devices fabricated on WSe2/hBN films show improved optical and electrical properties compared to films grown on sapphire under similar conditions. Our results reveal an important nucleation mechanism for the epitaxial growth of van der Waals heterostructures and demonstrate hBN as a superior substrate for single-crystal transition-metal dichalcogenide (TMD) films, resulting in a reduced density of IDBs and improved properties. The results motivate further efforts focused on the development of single crystal hBN substrates and epilayers for synthesis of wafer-scale single crystal TMD films.

Mobility Deception in Nanoscale Transistors: An Untold Contact Story.

Mobility is a critical parameter that is routinely used for benchmarking the performance of field-effect transistors (FETs) based on novel nanomaterials. In fact, mobility values are often used to champion nanomaterials since high-performance devices necessitate high mobility values. The current belief is that the contacts can only limit the FET performance and hence the extracted mobility is an underestimation of the true channel mobility. However, here, such misconception is challenged through rigorous experimental effort, backed by numerical simulations, to demonstrate that overestimation of mobility occurs in commonly used geometries and in nanomaterials for which the contact interface, contact doping, and contact geometry play a pivotal role. In particular, dual-gated FETs based on multilayer MoS2 and WSe2 are used as case studies in order to elucidate and differentiate between intrinsic and extrinsic contact effects manifesting in the mobility extraction. The choice of 2D layered transition metal dichalcogenides (TMDCs) as the semiconducting channel is motivated by their potential to replace and/or coexist with Si-based aging FET technologies. However, the results are equally applicable to nanotube- and nanowire-based FETs, oxide semiconductors, and organic-material-based thin-film FETs.

Defect Dynamics in 2-D MoS2 Probed by Using Machine Learning, Atomistic Simulations, and High-Resolution Microscopy.

Structural defects govern various physical, chemical, and optoelectronic properties of two-dimensional transition-metal dichalcogenides (TMDs). A fundamental understanding of the spatial distribution and dynamics of defects in these low-dimensional systems is critical for advances in nanotechnology. However, such understanding has remained elusive primarily due to the inaccessibility of (a) necessary time scales via standard atomistic simulations and (b) required spatiotemporal resolution in experiments. Here, we take advantage of supervised machine learning, in situ high-resolution transmission electron microscopy (HRTEM) and molecular dynamics (MD) simulations to overcome these limitations. We combine genetic algorithms (GA) with MD to investigate the extended structure of point defects, their dynamical evolution, and their role in inducing the phase transition between the semiconducting (2H) and metallic (1T) phase in monolayer MoS2. GA-based structural optimization is used to identify the long-range structure of randomly distributed point defects (sulfur vacancies) for various defect densities. Regardless of the density, we find that organization of sulfur vacancies into extended lines is the most energetically favorable. HRTEM validates these findings and suggests a phase transformation from the 2H-to-1T phase that is localized near these extended defects when exposed to high electron beam doses. MD simulations elucidate the molecular mechanism driving the onset of the 2H to 1T transformation and indicate that finite amounts of 1T phase can be retained by increasing the defect concentration and temperature. This work significantly advances the current understanding of defect structure/evolution and structural transitions in 2D TMDs, which is crucial for designing nanoscale devices with desired functionality.

Contact engineering for 2D materials and devices.

Over the past decade, the field of two-dimensional (2D) layered materials has surged, promising a new platform for studying diverse physical phenomena that are scientifically intriguing and technologically relevant. Contacts are the communication links between these 2D materials and the three-dimensional world for probing and harnessing their exquisite electronic properties. However, fundamental challenges related to contacts often limit the ultimate performance and potential of 2D materials and devices. This article provides a comprehensive overview of the basic understanding and importance of contacts to 2D materials and various strategies for engineering and improving them. In particular, we elucidate the phenomenon of Fermi level pinning at the metal/2D contact interface, the Schottky versus Ohmic nature of the contacts and various contact engineering approaches including interlayer contacts, phase engineered contacts, and basal versus edge plane contacts, among others. Finally, we also discuss some of the relatively under-addressed and unresolved issues, such as contact scaling, and conclude with a future outlook.

Superior Electro-Oxidation and Corrosion Resistance of Monolayer Transition Metal Disulfides.

Physics of monolayer and few-layer transition metal dichalcogenides (TMDs) and chemistry of few-layer TMDs have been well studied in recent years in the context of future electronic, optoelectronic, and energy harvesting applications. However, what has escaped the attention of the scientific community is the unique chemistry of monolayer TMDs. It has been demonstrated that the basal plane of multilayer TMDs is chemically inert, whereas edge sites are chemically active. In this article, we experimentally demonstrate that the edge reactivity of the TMDs can be significantly impeded at the monolayer limit through monolayer/substrate interaction, thus making the monolayers highly resistant to electrooxidation and corrosion. In particular, we found that few-layer flakes of MoS2 and WS2 exfoliated on conductive TiN substrates are readily corroded beyond a certain positive electrode potential, while monolayer remnants are left behind unscathed. The electrooxidation resistance of monolayers was confirmed using a plethora of characterization techniques including atomic force microscope (AFM) imaging, Raman spectroscopy, photoluminescence (PL) mapping, scanning/transmission electron microscope (S/TEM) imaging, and selected area electron diffraction (SAED). It is believed that strong substrate monolayer interaction compared to the relatively weak interlayer van der Waals interaction is responsible for the superior monolayers chemical stability in highly corrosive oxidizing environments. Our findings could pave the way for the implementation of monolayer transition metal disulfides as superior anticorrosion coating which can have a significant socioeconomic impact.

Facile Electrochemical Synthesis of 2D Monolayers for High-Performance Thin-Film Transistors.

In this paper, we report high-performance monolayer thin-film transistors (TFTs) based on a variety of two-dimensional layered semiconductors such as MoS2, WS2, and MoSe2 which were obtained from their corresponding bulk counterparts via an anomalous but high-yield and low-cost electrochemical corrosion process, also referred to as electro-ablation (EA), at room temperature. These monolayer TFTs demonstrated current ON-OFF ratios in excess of 107 along with ON currents of 120 µA/µm for MoS2, 40 µA/µm for WS2, and 40 µA/µm for MoSe2 which clearly outperform the existing TFT technologies. We found that these monolayers have larger Schottky barriers for electron injection compared to their multilayer counterparts, which is partially compensated by their superior electrostatics and ultra-thin tunnel barriers. We observed an Anderson type semiconductor-to-metal transition in these monolayers and also discussed possible scattering mechanisms that manifest in the temperature dependence of the electron mobility. Finally, our study suggests superior chemical stability and electronic integrity of monolayers even after being exposed to extreme electro-oxidation and corrosion processes which is promising for the implementation of such TFTs in harsh environment sensing. Overall, the EA process proves to be a facile synthesis route offering higher monolayer yields than mechanical exfoliation and lower cost and complexity than chemical vapor deposition methods.

Anomalous Corrosion of Bulk Transition Metal Diselenides Leading to Stable Monolayers.

In this paper we provide insight into an anomalous corrosion process, referred to as electroablation (EA), which converts multilayer flakes of transition metal diselenides like MoSe2 into their corresponding monolayers when micromechanically exfoliated on a conductive electrode and subsequently subjected to a high anodic potential inside a conventional electrochemical cell. Photoluminescence intensity maps and scanning transmission electron microscopy (STEM) images confirmed the single crystalline nature and 2H-hexagonal lattice structure of the remnant monolayer MoSe2 flakes, indicating the superior corrosion stability of the monolayers compared to that of the bulk counterpart. It is noted that the EA technique is a low-cost alternative for high-yield synthesis of single crystalline monolayer MoSe2 at room temperature. We also found that the dynamics of such an electro-oxidation-mediated and self-limiting corrosion process differs significantly for MoSe2 and WSe2. While we were able to engineer the corrosion conditions for the EA process to obtain monolayers of MoSe2, our attempts to obtain monolayers of WSe2 were largely unsuccessful. Finally, we constructed a phenomenological physical chemistry framework to explain such anomalous corrosion processes in transition metal diselenides.

Titanium dioxide nanowire sensor array integration on CMOS platform using deterministic assembly.

Nanosensor arrays have recently received significant attention due to their utility in a wide range of applications, including gas sensing, fuel cells, internet of things, and portable health monitoring systems. Less attention has been given to the production of sensor platforms in the µW range for ultra-low power applications. Here, we discuss how to scale the nanosensor energy demand by developing a process for integration of nanowire sensing arrays on a monolithic CMOS chip. This work demonstrates an off-chip nanowire fabrication method; subsequently nanowires link to a fused SiO2 substrate using electric-field assisted directed assembly. The nanowire resistances shown in this work have the highest resistance uniformity reported to date of 18%, which enables a practical roadmap towards the coupling of nanosensors to CMOS circuits and signal processing systems. The article also presents the utility of optimizing annealing conditions of the off-chip metal-oxides prior to CMOS integration to avoid limitations of thermal budget and process incompatibility. In the context of the platform demonstrated here, directed assembly is a powerful tool that can realize highly uniform, cross-reactive arrays of different types of metal-oxide nanosensors suited for gas discrimination and signal processing systems.

Mimicking Neurotransmitter Release in Chemical Synapses via Hysteresis Engineering in MoS2 Transistors.

Neurotransmitter release in chemical synapses is fundamental to diverse brain functions such as motor action, learning, cognition, emotion, perception, and consciousness. Moreover, improper functioning or abnormal release of neurotransmitter is associated with numerous neurological disorders such as epilepsy, sclerosis, schizophrenia, Alzheimer's disease, and Parkinson's disease. We have utilized hysteresis engineering in a back-gated MoS2 field effect transistor (FET) in order to mimic such neurotransmitter release dynamics in chemical synapses. All three essential features, i.e., quantal, stochastic, and excitatory or inhibitory nature of neurotransmitter release, were accurately captured in our experimental demonstration. We also mimicked an important phenomenon called long-term potentiation (LTP), which forms the basis of human memory. Finally, we demonstrated how to engineer the LTP time by operating the MoS2 FET in different regimes. Our findings could provide a critical component toward the design of next-generation smart and intelligent human-like machines and human-machine interfaces.