2D Channel Materials Research Articles

Ultra-High-k Ferroelectric BaTiO3 Perovskite in the Gate Stack for Two-Dimensional WSe2 p-Type High-Performance Transistors.

The experimental demonstration of a p-type 2D WSe2 transistor with a ferroelectric perovskite BaTiO3 gate oxide is presented. The 30 nm thick BaTiO3 gate stack shows a robust ferroelectric hysteresis with a remanent polarization of 20 μC/cm2 and further enables a capacitance equivalent thickness of 0.5 nm in the hybrid WSe2/BaTiO3 stack due to its high dielectric constant of 323. We demonstrate one of the best ON currents for perovskite gate 2D transistors in the literature. This is enabled by high-quality epitaxial growth of BaTiO3 and a single 2D layer transfer based fabrication method that is shown to be amenable to silicon platforms. This demonstration is an important milestone toward the integration of crystalline complex oxides with 2D channel materials for scaled CMOS and low-voltage ferroelectric logic applications.

Two-Dimensional Semiconductors for State-of-the-Art Complementary Field-Effect Transistors and Integrated Circuits.

As the trajectory of transistor scaling defined by Moore's law encounters challenges, the paradigm of ever-evolving integrated circuit technology shifts to explore unconventional materials and architectures to sustain progress. Two-dimensional (2D) semiconductors, characterized by their atomic-scale thickness and exceptional electronic properties, have emerged as a beacon of promise in this quest for the continued advancement of field-effect transistor (FET) technology. The energy-efficient complementary circuit integration necessitates strategic engineering of both n-channel and p-channel 2D FETs to achieve symmetrical high performance. This intricate process mandates the realization of demanding device characteristics, including low contact resistance, precisely controlled doping schemes, high mobility, and seamless incorporation of high- κ dielectrics. Furthermore, the uniform growth of wafer-scale 2D film is imperative to mitigate defect density, minimize device-to-device variation, and establish pristine interfaces within the integrated circuits. This review examines the latest breakthroughs with a focus on the preparation of 2D channel materials and device engineering in advanced FET structures. It also extensively summarizes critical aspects such as the scalability and compatibility of 2D FET devices with existing manufacturing technologies, elucidating the synergistic relationships crucial for realizing efficient and high-performance 2D FETs. These findings extend to potential integrated circuit applications in diverse functionalities.

High-Yield Production of High-κ/Metal Gate Nanopattern Array for 2D Devices via Oxidation-Assisted Etching Approach.

2D materials with atomically thin nature are promising to develop scaled transistors and enable the extreme miniaturization of electronic components. However, batch manufacturing of top-gate 2D transistors remains a challenge since gate dielectrics or gate electrodes transferred from 2D material easily peel away as gate pitch decreases to the nanometer scale during lift-off processes. In this study, an oxidation-assisted etching technique is developed for batch manufacturing of nanopatterned high-κ/metal gate (HKMG) stacks on 2D materials. This strategy produces nano-pitch self-oxidized Al2O3/Al patterns with a resolution of 150nm on 2D channel material, including graphene, MoS2, and WS2 without introducing any additional damage. Through a gate-first technology in which the Al2O3/Al gate stacks are used as a mask for the formation of source and drain, a short-channel HKMG MoS2 transistor with a nearly ideal subthreshold swing (SS) of 61mVdec-1, and HKMG graphene transistor with a cut-off frequency of 150GHz are achieved. Moreover, both graphene and MoS2 HKMG transistor arrays exhibit high uniformity. The study may bring the potential for the massive production of large-scale integrated circuits using 2D materials.

Compact modeling of short-channel effects in back-gated 2D negative capacitance (NC) FETs

The negative capacitance field-effect transistor with 2D channel material (2D NC-FET) holds significant promise for low-power applications owing to its remarkable resilience against short-channel effects (SCEs) and favorable noise characteristics. In this study, we establish a compact current–voltage (I–V) model for short-channel back-gated 2D NC-FETs with metal-ferroelectric-metal–insulator–semiconductor structure by self-consistently solving the two-dimensional Poisson, drift–diffusion and Landau–Khalatnikov equations. The proposed model is valid and continuous throughout the entire operating regime, including the fully-depleted region, partly-depleted region, and accumulation region. Furthermore, we derive analytical equations for the threshold voltage ( VTH ) and subthreshold swing ( SS ) of back-gated 2D NC-FETs based on the developed I–V model. Lastly, we elucidate the influence mechanisms of various device parameters and voltage bias on the subthreshold characteristics of short-channel back-gated 2D NC-FETs using the proposed I–V model in conjunction with analytical expressions of VTH and SS . Our findings reveal that back-gated 2D NC-FETs shows unconventional degradation behavior in VTH and SS, resulting from the competition between traditional SCEs and novel negative capacitance effects.

Two‐Dimensional Memtransistors for Non‐Von Neumann Computing: Progress and Challenges

AbstractThe increased demand of high‐performance computing systems has exposed the inherent limitations of the current state‐of‐the‐art von Neumann architecture. Therefore, developing alternate computing primitives that can offer faster computing speed with low energy expenditure is critical. In this context, while several non‐volatile memory (NVM) devices such as synaptic transistors, spintronic devices, phase change memory (PCM), and memristors have been demonstrated in the past, their two‐terminal nature necessitates additional peripheral elements that increase area and energy overhead. Recently, a new multiterminal device prototype known as a memtransistor has shown tremendous potential to overcome these limitations through exceptional control of the gate electrostatics as enabled by 2D channel materials. In this perspective, a brief overview of recent developments in 2D‐memtransistor devices is provided, including their fundamental operational mechanisms and the role of defects in enabling multiple NVM states and optical photoresponse. An overview of their implementation in the context of neuromorphic, probabilistic, information security, and edge‐sensing primitives is also provided. Finally, a futuristic perspective is provided looking toward their successful large‐scale technological integration.

Constructing 2D channel catalysts with accessible open transport channels for boosting epoxidation of methyl oleate

For the epoxidation of methyl oleate (MO), slow chemical reaction rate resulted from poor mass transfer remains a tough problem. Herein, we demonstrate a series of efficient 2D channel catalysts with accessible open transport channels, which provides an idea strategy for boosting epoxidation of MO and shortening its reaction time. 2D channel catalysts (2D-CSx-NH2-HPA) are fabricated by immobilizing heteropoly acid (HPA) on aminopropyl-functionalized 2D channel silica (2D-CSx-NH2), in which HPA is highly dispersed. These catalysts are applied to the epoxidation of MO, and the results show that the epoxidation performance of 2D channel catalysts for MO is related to its particle size and HPA types. As expected, the 2D-CS3.5-NH2-HPW with a length of 300 nm and an equatorial diameter of 150 nm exhibits outstanding catalytic activity (XMO = 91.68%) and epoxide selectivity (SEMO = 90.03%) with only 4 hours, which is much faster than that of majority of epoxidation catalysts reported so far. The excellent catalytic activity of 2D channel catalyst benefits from the appropriate pore width and particle size, which play an important role in exchanging substrates and dispersing active components. This study uses 2D channel catalyst to effectively shorten the reaction time of MO epoxidation, which paves a new avenue to develop other 2D channel materials for novel catalytic applications.

Unlocking performance potential of two-dimensional SnS2 transistors with solution-processed high-k Y:HfO2 film and semimetal bismuth contact

Two-dimensional (2D) tin disulfide (SnS2) is emerging as a viable channel material for high-performance field-effect transistors (FET) with high intrinsic mobility. To implement a high-performance two-dimensional SnS2 FET, high field-effect mobility (μFE), steep subthreshold swing (SS), high on-current value (Ion), and high on/off ratio (Ion/Ioff) must be realized. To improve these parameters, we first fabricated a high-k (∼30.5) yttrium-doped hafnium dioxide (Y:HfO2) film through a solution process to suppress Coulomb electron scattering, and to enhance the semiconductor-dielectric interface with an efficient metal–oxygen framework and a very smooth (root mean square = 0.29 nm) surface. Second, we induced Fermi level depinning by introducing a semimetal bismuth (Bi) contact with a low density of states (DOS) at the Fermi level to suppress the metal-induced gap state (MIGS). Through these two strategies, the SnS2 FET obtained high μFE (60.5 cm2V-1s−1), the SS theoretical limit of 60 mV/dec, negligible Schottky barrier height, high normalized on-current (IonL/W) of 90.6 μA, and high Ion/Ioff of 3 × 107, demonstrating that SnS2 can be re-evaluated as a potentially effective 2D channel material.

Edge and Interface Resistances Create Distinct Trade-Offs When Optimizing the Microstructure of Printed van der Waals Thin-Film Transistors

Inks based on two-dimensional (2D) materials could be used to tune the properties of printed electronics while maintaining compatibility with scalable manufacturing processes. However, a very wide range of performances have been reported in printed thin-film transistors in which the 2D channel material exhibits considerable variation in microstructure. The lack of quantitative physics-based relationships between film microstructure and transistor performance limits the codesign of exfoliation, sorting, and printing processes to inefficient empirical approaches. To rationally guide the development of 2D inks and related processing, we report a gate-dependent resistor network model that establishes distinct microstructure-performance relationships created by near-edge and intersheet resistances in printed van der Waals thin-film transistors. The model is calibrated by analyzing electrical output characteristics of model transistors consisting of overlapping 2D nanosheets with varied thicknesses that are mechanically exfoliated and transferred. Kelvin probe force microscopy analysis on the model transistors leads to the discovery that the nanosheet edges, not the intersheet resistance, limit transport due to their impact on charge carrier depletion and scattering. Our model suggests that when transport in a 2D material network is limited by the near-edge resistance, the optimum nanosheet thickness is dictated by a trade-off between charged impurity screening and gate screening, and the film mobilities are more sensitive to variations in printed nanosheet density. Removal of edge states can enable the realization of higher mobilities with thinner nanosheets due to reduced junction resistances and reduced gate screening. Our analysis of the influence of nanosheet edges on the effective film mobility not only examines the prospects of extant exfoliation methods to achieve the optimum microstructure but also provides important perspectives on processes that are essential to maximizing printed film performance.

Facile one-pot iodine gas phase doping on 2D MoS2/CuS FET at room temperature

Electronic devices composed of semiconducting two-dimensional (2D) materials and ultrathin 2D metallic electrode materials, accompanying synergistic interactions and extraordinary properties, are becoming highly promising for future flexible and transparent electronic and optoelectronic device applications. Unlike devices with bulk metal electrode and 2D channel materials, devices with ultrathin 2D electrode and 2D channel are susceptible to chemical reactions in both channel and electrode surface due to the high surface to volume ratio of the 2D structures. However, so far, the effect of doping was primary concerned on the channel component, and there is lack of understanding in terms of how to modulate electrical properties of devices by engineering electrical properties of both the metallic electrode and the semiconducting channel. Here, we propose the novel, one-pot doping of the field-effect transistor (FET) based on 2D molybdenum disulfide (MoS2) channel and ultrathin copper sulfide (CuS) electrodes under mild iodine gas environment at room temperature, which simultaneously modulates electrical properties of the 2D MoS2 channel and 2D CuS electrode in a facile and cost-effective way. After one-pot iodine doping, effective p-type doping of the channel and electrode was observed, which was shown through decreased off current level, improved I on/I off ratio and subthreshold swing value. Our results open up possibility for effectively and conveniently modulating electrical properties of FETs made of various 2D semiconductors and ultrathin contact materials without causing any detrimental damage.

Dependence of Tunneling Mechanism on Two-Dimensional Material Parameters: A High-Throughput Study

A band-to-band tunneling FET (TFET) with an atomical two-dimensional (2D) channel is a potential candidate for the next-generation electronic device in view of its steep subthreshold swing and low power consumption. However, how to establish a precise physical model between the band property of 2D channel materials and the device performance of 2D TFETs is the key to accelerate their practical applications. Herein, through high-throughput first-principles calculations, we study the tunneling transport properties of 44 representative 2D materials with four kinds of crystal system. Particularly, we propose a well-defined and striking exponential scaling law $(\mathrm{SS}=A{\mathrm{e}}^{B{m}_{r}}+C)$ between the subthreshold swings (SSs) and reduced effective masses $({m}_{r})$ of 10-nm TFETs. According to the exponential model, 2D orthorhombic and trigonal crystal TFETs with the steep SS hold the reduced effective masses of more than 0.1 and $0.2\phantom{\rule{0.25em}{0ex}}{m}_{0}$, which could inhibit tunneling leakage current. These insights provide guidance for material screening in the construction of post-Moore 2D low-power transistors.

Design of hierarchical self-assembly 2D silica and their derivative catalysts with accessible open transport channels for boosting oxidative-adsorptive desulfurization in fuel oil

The design and synthesis of hierarchical self-assembled 2D-channel silica (2D-CS) with mesoscopicshape control and developing of their application in catalysis has remained a challenge. Herein, we fabricated a series of 2D-CSx materials through the hierarchical self-assembly of curved lamellar micelles along with their derivative 2D channel catalysts (2D-CSx-NH2-HPW) by grafting amino groups and immobilizing phosphotungstic acid. These catalysts exhibit highly effective oxidative-adsorptive desulfurization (OADS) performance owing to their accessible open-transport channels. A novel theory that the stacking of curved lamellar micelles is similar to that of wrinkled-papers was proposed to explain the hierarchical self-assembly mechanism of the 2D-CS materials, which follows the “short-range order, long-range disorder” rule. Systematic characterizations and experiments indicated that the size and specific surface area of 2D-channel catalysts jointly determine their OADS performance. Most importantly, the 2D-channel catalysts show the highest removal efficiency of DBT when compared with 0D and 1D materials, which was ascribed to their facilitation of molecular diffusion owing to their accessible open-transport channels. The optimal 2D-channel catalysts (2D-CS4-NH2-HPW) exhibited excellent desulfurization performance despite omitting the extraction step, and the removal efficiency of DBT reached 99.72% in 5 min at 60 °C, much faster than previously reported mesoporous-catalyst-supported heteropoly acids. In addition, the OADS activity of typical sulfur compounds in the presence of the 2D-CSx-NH2-HPW catalyst was investigated, and the sulfur removal efficiency was found to decreases in the following order: DBT > 4,6-DMDBT > BT > n-DDM. The 2D-channel catalyst also exhibits excellent recyclability without significant loss of OADS activity after 10 cycles of reactions. This work provides a strategy for constructing 2D-channel catalysts for efficient desulfurization, demonstrating the potential of 2D-channel materials in catalytic applications.

Designing MoS2 channel properties for analog memory in neuromorphic applications

In this paper, we introduce analog nonvolatile random access memory cells for neuromorphic computing. The analog memory cell MoS2 channel is designed based on the simulation model including Fowler–Nordheim tunneling through a charge-trapping stack, trapping process, and transfer characteristics to describe a full write/read circle. 2D channel materials provide scaling to higher densities as well as preeminent modulation of the conductance by the accumulated space charge from the oxide trapping layer. In this paper, the main parameters affecting the distribution of memory states and their total number are considered. The dependence of memory state distribution on channel doping concentration and the number of layers is given. In addition, how the nonlinearity of memory state distribution can be overcome by variation of operating conditions and by applying pulse width modulation to the bottom gate voltage is also shown.

Asymmetric Chemical Functionalization of Top-Contact Electrodes: Tuning the Charge Injection for High-Performance MoS2 Field-Effect Transistors and Schottky Diodes.

The fabrication of high-performance (opto-)electronic devices based on 2D channel materials requires the optimization of the charge injection at electrode-semiconductor interfaces. While chemical functionalization with chemisorbed self-assembled monolayers has been extensively exploited to adjust the work function of metallic electrodes in bottom-contact devices, such a strategy has not been demonstrated for the top-contact configuration, despite the latter being known to offer enhanced charge-injection characteristics. Here, a novel contact engineering method is developed to functionalize gold electrodes in top-contact field-effect transistors (FETs) via the transfer of chemically pre-modified electrodes. The source and drain Au electrodes of the molybdenum disulfide (MoS2 ) FETs are functionalized with thiolated molecules possessing different dipole moments. While the modification of the electrodes with electron-donating molecules yields a marked improvement of device performance, the asymmetric functionalization of the source and drain electrodes with different molecules with opposed dipole moment enables the fabrication of a high-performance Schottky diode with a rectification ratio of ≈103 . This unprecedented strategy to tune the charge injection in top-contact MoS2 FETs is of general applicability for the fabrication of high-performance (opto-)electronic devices, in which asymmetric charge injection is required, enabling tailoring of the device characteristics on demand.

WSe2/WS2 Heterobilayer Nonvolatile Memory Device with Boosted Charge Retention.

A two-dimensional (2D) nonvolatile memory device architecture to improve the long-term charge retention with the minimum charge loss without compromising storage capacity and the extinction ratio for practical applications has been an imminent demand. To address the current issue, we adopted a novel type-II band-aligned heterobilayer channel comprising vertically stacked monolayer WSe2 nanodots on monolayer WS2. The band offset modulation leads to electron doping from WSe2 nanodots into the WS2 channel without any external driving electric field. As a result, the tested device outperformed with a memory window as high as 34 V and a negligible charge loss of 7% in a retention period of 10 years while maintaining a high extinction ratio of 106. The doping technique presented in this work provides a feasible route to modulate the electrical properties of 2D channel materials without hampering charge transport, paving the way for high-performance 2D memory devices.

Promising Properties of a Sub-5-nm Monolayer MoSi2N4 Transistor

Two-dimensional (2D) semiconductors have attracted tremendous interests as natural passivation and atomically thin channels that could facilitate continued transistor scaling. However, air-stable 2D semiconductors with high performance were quite elusive. Recently, extremely air-stable MoSi2N4 monolayer had been successfully fabricated [Hong et al., Science 369, 670 (2020)]. To further reveal its potential applications in the sub-5 nm MOSFETs, there is an urgent need to develop integrated circuits. Here we report first-principles quantum transport simulations on the performance limits of n- and p-type sub-5 nm monolayer (ML) MoSi2N4 metal-oxide-semiconductor FETs (MOSFETs). We find that the on-state current in the MoSi2N4 MOSFETs can be effectively manipulated by the length of gate and underlap (UL), as well as the doping concentration. Very strikingly, we also find that the n-type devices the optimized on-state current can reach up to 1390 and 1025 uA/um for the high performance (HP) and low power (LP) applications, respectively, both of which satisfy the International Technology Roadmap for Semiconductors (ITRS) requirements. Whereas, the optimized on-state current can meet the LP application (348 uA/um) for the p-type devices. Finally, we find that the MoSi2N4 MOSFETs have ultra-low subthreshold swing and power delay product, which have potential to realize the high speed and low power consumption devices. Our results show that MoSi2N4 is an ideal 2D channel material for future competitive ultrascaled devices.

Modulation Doping: A Strategy for 2D Materials Electronics

It remains a remarkable challenge to develop practical techniques for controllable and nondestructive doping in two-dimensional (2D) materials for their use in electronics and optoelectronics. Here, we propose a modulation doping strategy, wherein the perfect n-/p-type channel layer is achieved by accepting/donating electrons from/to the defects inside an adjacent encapsulation layer. We demonstrate this strategy in the heterostructures of BN/graphene, BN/MoS2, where the previously believed useless deep defects, such as the nitrogen vacancy in BN, can provide free carriers to the graphene and MoS2. The carrier density is further modulated by engineering the surroundings of the encapsulation layer. Moreover, the defects and carriers are naturally separated in space, eliminating the effects of Coulomb impurity scattering and thus allowing high mobility in the 2D limit. This doping strategy provides a highly viable route to tune 2D channel materials without inducing any structural damage, paving the way for high-performance 2D nanoelectronic devices.

Ab initio perspective of ultra-scaled CMOS from 2D-material fundamentals to dynamically doped transistors

Using accurate dissipative DFT-NEGF atomistic-simulation techniques within the Wannier-Function formalism, we give a fresh look at the possibility of sub-10-nm scaling for high-performance complementary metal oxide semiconductor (CMOS) applications. We show that a combination of good electrostatic control together with high mobility is paramount to meet the stringent roadmap targets. Such requirements typically play against each other at sub-10-nm gate length for MOS transistors made of conventional semiconductor materials like Si, Ge, or III–V and dimensional scaling is expected to end ~12 nm gate-length (pitch of 40 nm). We demonstrate that using alternative 2D channel materials, such as the less-explored HfS2 or ZrS2, high-drive current down to ~6 nm is, however, achievable. We also propose a dynamically doped field-effect transistor concept, that scales better than its MOSFET counterpart. Used in combination with a high-mobility material such as HfS2, it allows for keeping the stringent high-performance CMOS on current and competitive energy-delay performance, when scaling down to virtually 0 nm gate length using a single-gate architecture and an ultra-compact design (pitch of 22 nm). The dynamically doped field-effect transistor further addresses the grand-challenge of doping in ultra-scaled devices and 2D materials in particular.

Reliable and highly sensitive biosensor from suspended MoS2 atomic layer on nano-gap electrodes

The uneven morphology and the trapped charges at the surface of the traditionally used supporting substrate-based 2D biosensors produces a scattering effect, which leads to a irregular signals from individually fabricated devices. Though suspended 2D channel material has the potential to overcome scattering effects from the substrates but achieving reliability and selectivity, have been limiting the using of this biosensor technology. Here, we have demonstrated nanogap electrodes fabrication by using the self-assembly technique, which provides suspension to the 2D-MoS2. These nano-spacing electrodes not only give suspension but also provide robustness strength to the atomic layer, which remains freestanding after coating of the Hafnium oxide (HfO2) as well as linkers and antibodies. For evaluating the electrical characteristics of suspended MoS2 FET, gating potential was applied through an electrolyte on the suspended MoS2 transistor. This helped in achieved a lower subthreshold swing 70 mV/dec and ON/OFF ratio 107. Later, pH detection was conducted at room temperature, which showed an impressive sensitivity of ~880 by changing 1 unit of pH. We have also successfully shown Escherichia coli (E. coli) bacteria sensing from the suspended MoS2 transistor by functionalizing dielectric layer with E. coli antibodies. The reported biosensor has shown the ~9% of conductance changes with a lower concentration of E. coli (10 CFU/mL; colony-forming unit per mL) as well as maintain the constant sensitivity in three fabricated devices. The obtained enhancement in the sensitivity of devices and its effect on biomolecules detection can be extened to other biomolecules and this type of architecture has the potential to detect COVID-19 viruses based biomolecules.

Photochemically Induced Phase Change in Monolayer Molybdenum Disulfide.

Monolayer transition metal dichalcogenide (TMDs) are promising candidates for two-dimensional (2D) ultrathin, flexible, low-power, and transparent electronics and optoelectronics. However, the performance of TMD-based devices is still limited by the relatively low carrier mobility and the large contact resistance between the semiconducting 2D channel material and the contact metal electrodes. Phase-engineering in monolayer TMDs showed great promise in enabling the fabrication of high-quality hetero-phase structures with controlled carrier mobilities and heterojunction materials with reduced contact resistance. However, to date, general methods to induce phase-change in monolayer TMDs either employ highly-hostile organometallic compounds, or have limited compatibility with large-scale, cost-effective device fabrication. In this paper, we report a new photochemical method to induce semiconductor to metallic phase transition in monolayer MoS2 in a benign chemical environment, through a bench-top, cost-effective solution phase process that is compatible with large-scale device fabrication. It was demonstrated that photoelectrons produced by the band-gap absorption of monolayer MoS2 have enough chemical potential to activate the phase transition in the presence of an electron-donating solvent. This novel photochemical phase-transition mechanism advances our fundamental understanding of the phase transformation in 2D transition metal dichalcogenides (TMDs), and will open new revenues in the fabrication of atomically-thick metal-semiconductor heterostructures for improved carrier mobility and reduced contact resistance in TMD-based electronic and optoelectronic devices.

Nanodomain Engineering for Programmable Ferroelectric Devices.

We introduce a concept of programmable ferroelectric devices composed of two-dimensional (2D) and ferroelectric (FE) materials. It enables precise modulation of the in-plane conductivity of a 2D channel material through nanoengineering FE domains with out-of-plane polarization. The functionality of these new devices has been demonstrated using field-effect transistors (FETs) fabricated with monolayer molybdenum disulfide (MoS2) channels on the Pb(Zr,Ti)O3 substrates. Using piezoresponse force microscopy (PFM), we show that local switching of FE polarization by a conductive probe can be used to tune the conductivity of the MoS2 channel. Specifically, patterning of the nanoscale domains with downward polarization creates conductive paths in a resistive MoS2 channel so that the conductivity of an FET is determined by the number and length of the paths connecting source and drain electrodes. In addition to the device programmability, we demonstrate the device ON/OFF cyclic endurance by successive writing and erasing of conductive paths in a MoS2 channel. These findings may inspire the development of advanced energy-efficient programmable synaptic devices based on a combination of 2D and FE materials.