Two-dimensional Layered Semiconductors Research Articles

Two-dimensional transistors with reconfigurable polarities for secure circuits

Security is a critical aspect in modern circuit design, but research into hardware security at the device level is rare as it requires modification of existing technology nodes. With the increasing challenges facing the semiconductor industry, interest in out-of-the-box security solutions has grown, even if this implies introducing novel materials such as two-dimensional layered semiconductors. Here, we show that high-performance, low-voltage, two-dimensional black phosphorus field-effect transistors (FETs) that have reconfigurable polarities are suitable for hardware security applications. The transistors can be dynamically switched between p-FET and n-FET operation through electrostatic gating and can achieve on–off ratios of 105 and subthreshold swings of 72 mV dec−1 at room temperature. Using the transistors, we create inverters that exhibit gains of 33.3 and are fully functional at a supply voltage of 0.2 V. We also create a security primitive circuit with polymorphic NAND/NOR obfuscation functionality with sub-1-V operation voltages, and the robustness of the polymorphic gate against power supply variations is tested using Monte Carlo simulations. Transistors that use two-dimensional black phosphorus as the active material can dynamically switch between p-type and n-type operation, and can be used to create security primitive circuits with polymorphic NAND/NOR obfuscation functionality.

Electron beam evaporated Au islands as a nanoscale etch mask on few-layer MoS2 and fabrication of top-edge hybrid contacts for field-effect transistors

Metal contacts to two-dimensional layered semiconductors are crucial to the performance of field-effect transistors (FETs) and other applications of layered materials in nanoelectronics and beyond. In this work, the wetting behavior of very thin Au films on exfoliated MoS2 flakes was studied and evaluated as a nanoscale, self-assembled dry etch mask. Etching nanoscale pits into MoS2 flakes prior to metallization from the top of the flake forms edge sites that contribute some fraction of edge contacts in addition to top contacts for additional carrier injection and lower contact resistance. The morphology and thickness of Au islands and MoS2 were studied with scanning electron microscopy and atomic force microscopy before and after etching with low-power plasmas. A Cl2 plasma etch of 10 s with a Au island mask of 6 nm (nominal) showed the best resulting morphology among the plasma conditions studied. Back-gated MoS2-based FETs on SiO2/p +-Si with Ti/Au contacts were fabricated using a Cl2 etch of only the contact regions, and they yielded devices with ON currents of 100s µA/µm, ON/OFF ratios ⩾106, and contact resistance <10 kΩ µm. The best set of devices had a very low contact resistance of ∼1 kΩ µm with almost no dependence of contact resistance on gating. Using nanoscale etch masks made from metal islands could be highly customizable and shows promise for engineering FETs with low contact resistance.

Highly stable all-in-one photoelectrochemical electrodes based on carbon nanowalls

Photoelectrochemical (PEC) cells offer a promising approach for developing low-cost solar energy conversion systems. However, the lack of stable and cost-effective electrodes remains a bottleneck that hampers their practical applications. Here, we propose a kind of integrated all-in-one three-dimensional (3D) carbon nanowall (CNW) electrode without sensitized semiconductors for stable all-carbon PEC cells. The all-in-one CNW electrodes were fabricated by directly growing CNW on both sides of the SiO2/Si/SiO2 wafer employing the radio frequency plasmon enhanced chemical vapor deposition method. Benefitting from the interconnected 3D textured structure, the CNW can effectively absorb the incident light and provide a large electrochemical reaction interface at the CNW surface that promotes the separation of photogenerated charge carriers, which makes it a superior electrode material. Experimental results show that the all-in-one CNW electrodes possess excellent PEC performance with a photocurrent density of 830 μA cm−2. Moreover, the CNW electrodes exhibit excellent photoresponses over a wide waveband and superior stability with a maintained photocurrent response, even after 60 d, which outperforms the electrodes using the other two-dimensional layered materials or semiconductor sensitized electrodes. Such an all-in-one electrode with impressive photovoltaic properties provides a promising platform for PEC applications that is eco-friendly with high efficiency, excellent stability and low cost.

Pressure-induced evolution of band structure in black phosphorus studied by P31 NMR

Two-dimensional layered semiconductor black phosphorus (BP), a promising pressure induced Dirac system as predicted by band structure calculations, has been studied by $^{31}$P-nuclear magnetic resonance. Band calculations have been also carried out to estimate the density of states $D(E)$. The temperature and pressure dependences of nuclear spin lattice relaxation rate $1/T_1$ in the semiconducting phase are well reproduced using the derived $D(E)$, and the resultant pressure dependence of semiconducting gap is in good accordance with previous reports, giving a good confirmation that the band calculation on BP is fairly reliable. The present analysis of $1/T_1$ data with the complemental theoretical calculations allows us to extract essential information, such as the pressure dependences of $D(E)$ and chemical potential, as well as to decompose observed $1/T_1$ into intrinsic and extrinsic contributions. An abrupt increase in $1/T_1$ at 1.63GPa indicates that the semiconducting gap closes, resulting in an enhancement of conductivity.

Epitaxial nucleation and lateral growth of high-crystalline black phosphorus films on silicon

Black phosphorus (BP) is a promising two-dimensional layered semiconductor material for next-generation electronics and optoelectronics, with a thickness-dependent tunable direct bandgap and high carrier mobility. Though great research advantages have been achieved on BP, lateral synthesis of high quality BP films still remains a great challenge. Here, we report the direct growth of large-scale crystalline BP films on insulating silicon substrates by a gas-phase growth strategy with an epitaxial nucleation design and a further lateral growth control. The optimized lateral size of the achieved BP films can reach up to millimeters, with the ability to modulate thickness from a few to hundreds of nanometers. The as-grown BP films exhibit excellent electrical properties, with a field-effect and Hall mobility of over 1200 cm2V−1s−1 and 1400 cm2V−1s−1 at room temperature, respectively, comparable to those exfoliated from BP bulk crystals. Our work opens the door for broad applications with BP in scalable electronic and optoelectronic devices.

Unravelling the effect of sulfur vacancies on the electronic structure of the MoS2 crystal.

Molybdenum disulfide (MoS2) is one of the two-dimensional layered semiconductor transition metal dichalcogenides (TMDCs) with great potential in electronics, optoelectronics, and spintronic devices. Sulfur vacancies in MoS2 are the most prevalent defects. However, the effect of sulfur vacancies on the electronic structure of MoS2 is still in dispute. Here we experimentally and theoretically investigated the effect of sulfur vacancies in MoS2. The vacancies were intentionally introduced by thermal annealing of MoS2 crystals in a vacuum environment. Angle-resolved photoemission spectroscopy (ARPES) was used directly to observe the electronic structure of the MoS2 single crystals. The experimental result distinctly revealed the appearance of an occupied defect state just above the valence band maximum (VBM) and an upward shift of the VBM after creating sulfur vacancies. In addition, density functional theory (DFT) calculations also confirmed the existence of the occupied defect state close to the VBM as well as two deep unoccupied states induced by the sulfur vacancies. Our results provide evidence to contradict that sulfur vacancies indicate the origin of n-type behaviour in MoS2. This work provides a rational strategy for tuning the electronic structures of MoS2.

Optical Properties and Light-Emission Device Applications of 2-D Layered Semiconductors

Two-dimensional layered semiconductors have attracted a great deal of attention recently from many fields of science and technology. This article overviews the major progress from the perspective of light-emission properties and related device applications of such 2-D materials. We begin with the overview of basic optical properties, including emission features of various excitonic complexes, many-body effects, light-emission enhancement due to plasmonic coupling, and mechanisms of optical gain. This is followed by discussions of coupling of 2-D materials with an optical cavity, including cavity-enhanced emission due to the Purcell effect, strong and weak coupling, as well as lasing behavior. We then discuss the design and the fabrication of various heterostructures by stacking layers of different 2-D materials for the purpose of confining and injecting charge carriers. Such structures are indispensable for light-emitting devices under electrical injection, the ultimate goal of any semiconductor-based light-emitting diode (LED) or lasers. The progress in electrical injection devices is reviewed next, where LEDs under lateral and vertical electrical injection schemes are discussed. The review is concluded with an outlook and future perspectives.

Stable InSe transistors with high-field effect mobility for reliable nerve signal sensing

Among two-dimensional layered semiconductors, indium selenide (InSe) is one of the most promising materials with absolute advantages in field-effect transistors (FETs) because of its high electron mobility and stable material properties. Some work has been performed to improve the mobility of InSe FETs. However, in practical applications, electrical stability of FETs is another essential factor to guarantee the performance of the electronic system. Here, we show a highly stable InSe FET with a field-effect mobility of 1200 cm2/V·s in the practical working regime. The bottom-gate staggered InSe FET was fabricated with a polymethyl methacrylate (PMMA)/HfO2 dual-layer gate dielectric and PMMA back-channel encapsulation. The hysteresis was maintained at 0.4 V after 30 days of storage under normal ambient conditions, and the threshold voltage shift was retained at 0.6 V with a gate stress VGS of 10 V, which represents the best electrical stability reported to date. Its high mobility and electrical stability enable reliable detection of the weak nerve action potential at a low power consumption. High-performance InSe FETs expand their promising applications in flexible and in situ real-time intelligent nerve action potential recording.

Accurate Threshold Voltage Reliability Evaluation of Thin Al2O3 Top-Gated Dielectric Black Phosphorous FETs Using Ultrafast Measurement Pulses.

Few-layer black phosphorus (BP) has attracted significant interest in recent years due to electrical and photonic properties that are far superior to those of other two-dimensional layered semiconductors. The study of long term electrical stability and reliability of black phosphorus field effect transistors (BP-FETs) with technologically relevant thin, and device-selective, gate dielectrics, stressed under realistic (closer to operation) bias and measured using state-of-the-art ultrafast reliability characterization techniques, is essential for their qualification and use in different applications. In this work, air-stable BP-FETs with a thin top-gated dielectric (15 nm Al2O3, SiO2 equivalent thickness of 5 nm) were fabricated and comprehensively characterized for threshold voltage ( Vth) instability under negative gate bias stress at various measurement delays ( tm), stress biases ( VGSTR), temperatures ( T), and stress times ( tstr) for the first time. Thin top-gated oxide enables low VGSTR that is closer to the operating condition and ultrafast Vth measurements with low delay ( tm = 10 μs, due to high drain current) that ensure minimal recovery. The resultant time kinetics of Vth degradation (Δ Vth) shows fast saturation at longer stress times and low-temperature activation energy. Vth instability in these top-gated devices is suggested to be dominated by hole trapping, which is modeled using first-order equations at different VGSTR and T. It is shown that measurements using larger tm show lower degradation magnitude that do not saturate due to recovery artifacts and give inaccurate estimation of hole trap densities. Conventional, thick, and global back-gated oxide BP-FETs were also fabricated and characterized for varying tm (1 ms being the lowest due to a low drain current level for thick oxide), VGSTR, and T to benchmark our top-gated results. Nonsaturating Δ Vth in the back-gated devices is shown to result from recovery artifacts due to the large tm (1 ms and greater) values. Finally, using a VGSTR and T-dependent first-order model, we show that the top-gated Al2O3 BP-FETs with scaled gate oxide thickness can match state-of-the-art Si reliability specifications at operating voltage and room/elevated temperature.

Proximity-Induced Colossal Conductivity Modulation in Phosphorene

Phosphorene is a promising single elemental two-dimensional layered semiconductor with huge potential for future nanoelectronics and spintronics applications. In this work, we investigated the effect of an organic molecule (benzene) in the close proximity of a Phosphorene nanoribbon. Our extensive calculations reveal that the semiconducting nature of Phosphorene stays unaffected as a result of the molecular adsorption while the transport properties go through drastic changes. Under the influence of dopant atoms and external strain, colossal changes in the conductivity is observed with a maximum enhancement > 1500% which has not been observed earlier. This effect is pretty robust against the (i) variation of system size, (ii) type, location and concentration of dopants and (iii) nature and magnitude of the external strain. Furthermore, we demonstrated how a gate voltage can be used to fine tune the enhanced conductivity response in a Field-effect transistor (FET) structure. Our results provide new direction for Phosphorene based nanoelectronics in applications like sensing, switching where a higher level of conduction can offer better resolution, higher ON/OFF ratio and superior energy efficiency.

Experimental Identification of Critical Condition for Drastically Enhancing Thermoelectric Power Factor of Two-Dimensional Layered Materials.

Nanostructuring is an extremely promising path to high-performance thermoelectrics. Favorable improvements in thermal conductivity are attainable in many material systems, and theoretical work points to large improvements in electronic properties. However, realization of the electronic benefits in practical materials has been elusive experimentally. A key challenge is that experimental identification of the quantum confinement length, below which the thermoelectric power factor is significantly enhanced, remains elusive due to lack of simultaneous control of size and carrier density. Here we investigate gate-tunable and temperature-dependent thermoelectric transport in γ-phase indium selenide (γ-InSe, n-type semiconductor) samples with thickness varying from 7 to 29 nm. This allows us to properly map out dimension and doping space. Combining theoretical and experimental studies, we reveal that the sharper pre-edge of the conduction-band density of states arising from quantum confinement gives rise to an enhancement of the Seebeck coefficient and the power factor in the thinner InSe samples. Most importantly, we experimentally identify the role of the competition between quantum confinement length and thermal de Broglie wavelength in the enhancement of power factor. Our results provide an important and general experimental guideline for optimizing the power factor and improving the thermoelectric performance of two-dimensional layered semiconductors.

Perfect absorption in transition metal dichalcogenides-based dielectric grating

The low absolute absorption of monolayer transition metal dichalcogenide severely restricts their available applications due to its atomic thickness, despite their large absorption coefficients. We investigate theoretically, the absorption properties of a hybrid structure which combines dielectric grating and photonic crystal together, where monolayer transition metal dichalcogenide is placed on the top. The guide mode resonances associated with waveguide mode resonances grant the multifold enhancement of the absorption of the hybrid structure, leading to two perfect absorption peaks as well as another high absorption peak with the amplitude of 95%. In particular, strong absorption of the hybrid structure with monolayer transition metal dichalcogenide appears in the visible frequency regime. This is in contrast to those with monolayer graphene always in terahertz and near-infrared range and facilitates their promising applications in photodetectors or solar cells. Our findings offer monolayer transition metal dichalcogenide unique opportunities for applications in optoelectronics and nano-photonics devices and this strategy of achieving high absorption can be applicable to other two-dimensional layered semiconductors.

Raman Spectra and Strain Effects in Bismuth Oxychalcogenides

A new type of two-dimensional layered semiconductor with weak electrostatic but not van der Waals interlayer interactions, Bi2O2Se, has been recently synthesized, which shown excellent air stability and ultrahigh carrier mobility. Herein, we combined theoretical and experimental approaches to study the Raman spectra of Bi2O2Se and related bismuth oxychalcogenides (Bi2O2Te and Bi2O2S). The experimental peaks were fully consistent with the calculated results, and were successfully assigned. Bi2O2S was predicted to have more Raman-active modes due to its lower symmetry. The shift of the predicted frequencies of Raman active modes was also found to get softened as the interlayer interaction decreases from bulk to monolayer Bi2O2Se and Bi2O2Te. To reveal the strain effects on the Raman shifts, a universal theoretical equation was established based on the symmetry of Bi2O2Se and Bi2O2Te. It was predicted that the doubly degenerate modes split under in-plane uniaxial/shear strains. Under a rotated uniaxial strain, the changes of Raman shifts are anisotropic for degenerate modes although Bi2O2Se and Bi2O2Te were usually regarded as isotropic systems similar to graphene. This implies a novel method to identify the crystallographic orientation from Raman spectra under strain. These results have important consequences for the incorporation of 2D Bismuth oxychalcogenides into nanoelectronic devices.

Boosting heterojunction interaction in electrochemical construction of MoS2 quantum dots@TiO2 nanotube arrays for highly effective photoelectrochemical performance and electrocatalytic hydrogen evolution

MoS2 quantum dots (QDs) are loaded onto TiO2 nanotube arrays (NTAs) via a facile strategy of combining electrochemical exfoliation with electrophoretic deposition (EFED). The optimal MoS2@TiO2 NTAs exhibits a low onset potential (76 mV vs RHE) with the Tafel slope of 93 mV dec−1. The reported synthesis strategy is suitable for the heterojunction construction of other two-dimensional layered materials and semiconductor composites with excellent photoelectric properties.

Enhanced photoresponsivity and hole mobility of MoTe2 phototransistors by using an Al2O3 high-κ gate dielectric

Molybdenum ditelluride (MoTe2) has been demonstrated great potential in electronic and optoelectronic applications. However, the reported effective hole mobility remains far below its theoretical value. Herein, taking advantage of high-κ screening effect, we have fabricated back-gated MoTe2 transistors on an Al2O3 high-κ dielectric and systematically investigated the electronic and optoelectronic properties. A high current on/off ratio exceeding 106 is achieved in the Al2O3-based MoTe2 transistors, and the hole mobility is demonstrated to be 150 cm2 V−1 s−1, compared to 0.2–20 cm2 V−1 s−1 ever obtained from back-gated MoTe2 transistors in the literatures. Moreover, a considerable hole concentration of 1.2 × 1013 cm−2 is attained in our Al2O3-based MoTe2 transistors owing to the strong gate control capability, leading to a high on-state hole current of 6.1 μA μm−1. After optimization, our Al2O3-based MoTe2 phototransistor exhibits outstanding photodetective performance, with a high responsivity of 543 A W−1 and a high photogain of 1,662 at 405 nm light illumination, which are boosted around 419 times compared to the referential SiO2-based control devices. The mechanisms of photoconductivity in the Al2O3-based MoTe2 phototransistors have been analyzed in detail, and the photogating effect is considered to play an important role. This work may provide useful insight to improve carrier mobility in two-dimensional layered semiconductors and open opportunities to facilitate the development of high-performance photodetectors in the future.

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.

Vertically Stacked and Self-Encapsulated van der Waals Heterojunction Diodes Using Two-Dimensional Layered Semiconductors.

van der Waals heterojunctions using 2D semiconducting materials could overcome the defect issues included by lattice mismatch in conventional epitaxially grown heterojunctions with bulk materials and could enable a much wider palette for choice of materials and more sophisticated device design. Such 2D heterojunction devices are of great interest for important functional devices such as diodes, bipolar junction transistors, light-emitting diodes, and photodetectors. In this paper, we demonstrate a truly vertical p-n heterojunction diode built from 2D semiconductors (MoS2 and BP) and compare its performance against conventional lateral 2D heterojunction devices (partially overlapped 2D heterostructures). Both vertical and lateral p-n heterostructure diodes exhibit a strong rectification ratio even with no gate voltage applied. More importantly, the results show that the vertical diode delivers 70 times higher current density under forward bias than a conventional lateral device design and the improved device performance can be attributed to the complete elimination of series resistance. Low-temperature measurements and TCAD simulations are used to determine the barrier height at the junctions. Moreover, the vertical device structure allows certain ambiently unstable 2D semiconductors to be fully encapsulated by the materials on top, preventing the material from degradation. This work demonstrates the potential of using the vertically stacked 2D semiconductors for future nanoelectronic and optoelectronic devices with optimal performance.

Anomalous Above-Gap Photoexcitations and Optical Signatures of Localized Charge Puddles in Monolayer Molybdenum Disulfide.

Broadband optoelectronics such as artificial light harvesting technologies necessitate efficient and, ideally, tunable coupling of excited states over a wide range of energies. In monolayer MoS2, a prototypical two-dimensional layered semiconductor, the excited state manifold spans the visible electromagnetic spectrum and is comprised of an interconnected network of excitonic and free-carrier excitations. Here, photoluminescence excitation spectroscopy is used to reveal the energetic and spatial dependence of broadband excited state coupling to the ground-state luminescent excitons of monolayer MoS2. Photoexcitation of the direct band gap excitons is found to strengthen with increasing energy, demonstrating that interexcitonic coupling across the Brillouin zone is more efficient than previously reported, and thus bolstering the import and appeal of these materials for broadband optoelectronic applications. Narrow excitation resonances that are superimposed on the broadband photoexcitation spectrum are identified and coincide with the energetic positions of the higher-energy excitons and the electronic band gap as predicted by first-principles calculations. Identification of such features outlines a facile route to measure the optical and electronic band gaps and thus the exciton binding energy in the more sophisticated device architectures that are necessary for untangling the rich many-body phenomena and complex photophysics of these layered semiconductors. In as-grown materials, the excited states exhibit microscopic spatial variations that are characteristic of local carrier density fluctuations, similar to charge puddling phenomena in graphene. Such variations likely arise from substrate inhomogeneity and demonstrate the possibility to use substrate patterning to tune local carrier density and dynamically control excited states for designer optoelectronics.

Impact and Origin of Interface States in MOS Capacitor with Monolayer MoS2 and HfO2 High-k Dielectric

Two-dimensional layered semiconductors such as molybdenum disulfide (MoS2) at the quantum limit are promising material for nanoelectronics and optoelectronics applications. Understanding the interface properties between the atomically thin MoS2 channel and gate dielectric is fundamentally important for enhancing the carrier transport properties. Here, we investigate the frequency dispersion mechanism in a metal-oxide-semiconductor capacitor (MOSCAP) with a monolayer MoS2 and an ultra-thin HfO2 high-k gate dielectric. We show that the existence of sulfur vacancies at the MoS2-HfO2 interface is responsible for the generation of interface states with a density (Dit) reaching ~7.03 × 1011 cm−2 eV−1. This is evidenced by a deficit S:Mo ratio of ~1.96 using X-ray photoelectron spectroscopy (XPS) analysis, which deviates from its ideal stoichiometric value. First-principles calculations within the density-functional theory framework further confirms the presence of trap states due to sulfur deficiency, which exist within the MoS2 bandgap. This corroborates to a voltage-dependent frequency dispersion of ~11.5% at weak accumulation which decreases monotonically to ~9.0% at strong accumulation as the Fermi level moves away from the mid-gap trap states. Further reduction in Dit could be achieved by thermally diffusing S atoms to the MoS2-HfO2 interface to annihilate the vacancies. This work provides an insight into the interface properties for enabling the development of MoS2 devices with carrier transport enhancement.

Subthreshold swing improvement in MoS2 transistors by the negative-capacitance effect in a ferroelectric Al-doped-HfO2/HfO2 gate dielectric stack

Obtaining a subthreshold swing (SS) below the thermionic limit of 60 mV dec-1 by exploiting the negative-capacitance (NC) effect in ferroelectric (FE) materials is a novel effective technique to allow the reduction of the supply voltage and power consumption in field effect transistors (FETs). At the same time, two-dimensional layered semiconductors, such as molybdenum disulfide (MoS2), have been shown to be promising candidates to replace silicon MOSFETs in sub-5 nm-channel technology nodes. In this paper, we demonstrate NC MoS2 FETs by incorporating a ferroelectric Al-doped HfO2 (Al : HfO2), a technologically compatible material, in the FET gate stack. Al : HfO2 thin films were deposited on Si wafers by atomic layer deposition. Voltage amplification up to 1.25 times was observed in a FE bilayer stack of Al : HfO2/HfO2 with a Ni metallic intermediate layer. The minimum SS (SSmin) of the NC-MoS2 FET built on the FE bilayer improved to 57 mV dec-1 at room temperature, compared with SSmin = 67 mV dec-1 for the MoS2 FET with only HfO2 as a gate dielectric.