Liquid-Metal-Based Spin-Coating Exfoliation for Atomically Thin Metal Oxide Synthesis.

Two-dimensional (2D) semiconductors possess exceptional electronic, optical, and magnetic properties, making them highly desirable for widespread applications. However, conventional mechanical exfoliation and epitaxial growth methods are insufficient in meeting the demand for atomically thin films covering large areas while maintaining high quality. Herein, leveraging liquid metal oxidation reaction, we propose a motorized spin-coating exfoliation strategy to efficiently produce large-area 2D metal oxide (2DMO) semiconductors with high crystallinity, atomically thin thickness, and flat surfaces on diverse substrates. Moreover, we realized a 2D gallium oxide-based deep ultraviolet solar-blind photodetector featuring a metal-semiconductor-metal structure, showcasing high responsivity (8.24 A W-1) at 254 nm and excellent sensitivity (4.3 × 1012 cm Hz1/2 W-1). This novel liquid-metal-based spin-coating exfoliation strategy offers great potential for synthesizing atomically thin 2D semiconductors, opening new avenues for future functional electronic and optical applications.

Influences of point defects on electron transport of two-dimensional gep semiconductor device.

The quantum transport properties of defective two-dimensional (2D) GeP semiconductor nanodevice consisting of typical point defects, such as antisite defect, substitutional defect, and Schottky defect, have been studied by using density functional theory combined with non-equilibrium Green's function calculation. The antisite defect has indistinctive influences on electron transport. However, both substitutional and Schottky defect have introduced promising defect state at the Fermi level, indicating the possibility of improvement on the carrier transport. Our quantitative quantum transport calculations ofI-Vbbehavior have revealed that the electrical characters are enhanced. Moreover, the P atom vacancy could induce significant negative differential resistance phenomenon, and the physical mechanism is unveiled by detailed analysis. The transfer characteristic properties could be prominently improved by substitutional defect and vacancy defect. Most importantly, we have proposed a computational design of GeP-based electronic device with improved electrical performance by introducing vacancy defect. Our findings could be helpful to the practical application of novel 2D GeP semiconductor nanodevice in future.

Synthesis of Fibrous Phosphorus Micropillar Arrays with Pyro-Phototronic Effects.

The bottom-up preparation of two-dimensional material micro-nano structures at scale facilitates the realisation of integrated applications in optoelectronic devices. Fibrous Phosphorus (FP), an allotrope of black phosphorus (BP), is one of the most promising candidate materials in the field of optoelectronics with its unique crystal structure and properties.[1] However, to date, there are no bottom-up micro-nano structure preparation methods for crystalline phosphorus allotropes.[1c, 2] Herein, we present the bottom-up preparation of fibrous phosphorus micropillar (FP-MP) arrays via a low-pressure gas-phase transport (LP-CVT) method that controls the directional phase transition from amorphous red phosphorus (ARP) to FP. In addition, self-powered photodetectors (PD) of FP-MP arrays with pyro-phototronic effects achieved detection beyond the band gap limit. Our results provide a new approach for bottom-up preparation of other crystalline allotropes of phosphorus.

Charged Exciton Kinetics in Monolayer MoSe2 near Ferroelectric Domain Walls in Periodically Poled LiNbO3.

Monolayer semiconducting transition metal dichalcogenides are a strongly emergent platform for exploring quantum phenomena in condensed matter, building novel optoelectronic devices with enhanced functionalities. Because of their atomic thickness, their excitonic optical response is highly sensitive to their dielectric environment. In this work, we explore the optical properties of monolayer thick MoSe2 straddling domain wall boundaries in periodically poled LiNbO3. Spatially resolved photoluminescence experiments reveal spatial sorting of charge and photogenerated neutral and charged excitons across the boundary. Our results reveal evidence for extremely large in-plane electric fields of ≃4000 kV/cm at the domain wall whose effect is manifested in exciton dissociation and routing of free charges and trions toward oppositely poled domains and a nonintuitive spatial intensity dependence. By modeling our result using drift-diffusion and continuity equations, we obtain excellent qualitative agreement with our observations and have explained the observed spatial luminescence modulation using realistic material parameters.

Bandgap Engineering of Hydroxy-Functionalized Borophene for Superior Photo-Electrochemical Performance.

Two-dimensional (2D) semiconducting boron nanosheets (few-layer borophene) have been theoretically predicted, but their band gap tunability has not been experimentally confirmed. In this study, hydroxy-functionalized borophene (borophene-OH) with tunable band gap was fabricated by liquid-phase exfoliation using 2-butanol solvent. Surface-energy matching between boron and 2-butanol produced smooth borophene, and the exposed unsaturated B sites generated by B-B bond breaking during exfoliation coordinated with OH groups to form semiconducting borophene-OH, enabling a tunable band gap of 0.65-2.10 eV by varying its thickness. Photoelectrochemical (PEC) measurements demonstrated that the use of borophene-OH to fabricate working electrodes for PEC-type photodetectors significantly enhanced the photocurrent density (5.0 µA cm-2 ) and photoresponsivity (58.5 µA W-1 ) compared with other 2D monoelemental materials. Thus, borophene-OH is a promising semiconductor with great optoelectronic potential.

Two-dimensional mono-elemental semiconductor with electronically inactive defects: the case of phosphorus.

The deep gap states created by defects in semiconductors typically deteriorate the performance of (opto)electronic devices. This has limited the applications of two-dimensional (2D) metal dichalcogenides (MX2) and underscored the need for a new 2D semiconductor without defect-induced deep gap states. In this work, we demonstrate that a 2D mono-elemental semiconductor is a promising candidate. This is exemplified by first-principles study of 2D phosphorus (P), a recently fabricated high-mobility semiconductor. Most of the defects, including intrinsic point defects and grain boundaries, are electronically inactive, thanks to the homoelemental bonding, which is not preferred in heteroelemental system such as MX2. Unlike MX2, the edges of which create deep gap states and cannot be eliminated by passivation, the edge states of 2D P can be removed from the band gap by hydrogen termination. We further find that both the type and the concentration of charge carriers in 2D P can be tuned by doping with foreign atoms. Our work sheds light on the role of defects in the electronic structure of materials.

Adjustment methods of Schottky barrier height in one- and two-dimensional semiconductor devices.

The Schottky contact which is a crucial interface between semiconductors and metals is becoming increasingly significant in nano-semiconductor devices. A Schottky barrier, also known as the energy barrier, controls the depletion width and carrier transport across the metal-semiconductor interface. Controlling or adjusting Schottky barrier height (SBH) has always been a vital issue in the successful operation of any semiconductor device. This review provides a comprehensive overview of the static and dynamic adjustment methods of SBH, with a particular focus on the recent advancements in nano-semiconductor devices. These methods encompass the work function of the metals, interface gap states, surface modification, image-lowering effect, external electric field, light illumination, and piezotronic effect. We also discuss strategies to overcome the Fermi-level pinning effect caused by interface gap states, including van der Waals contact and 1D edge metal contact. Finally, this review concludes with future perspectives in this field.

Fundamental Understanding of Interface Chemistry and Electrical Contact Properties of Bi and MoS2.

The interface properties and thermal stability of bismuth (Bi) contacts on molybdenum disulfide (MoS2) shed light on their behavior under various deposition conditions and temperatures. The examination involves extensive techniques including X-ray photoelectron spectroscopy, scanning tunneling microscopy (STM), and scanning tunneling spectroscopy (STS). Bi contacts formed a van der Waals interface on MoS2 regardless of deposition conditions, such as ultrahigh vacuum (UHV, 3 × 10-11 mbar) and high vacuum (HV, 4 × 10-6 mbar), while the oxidation on MoS2 has been observed. However, the semimetallic properties of Bi suppress the impact of defect states, including oxidized-MoS2 and vacancies. Notably, the n-type characteristic of Bi/MoS2 remains unaffected, and no significant changes in the local density of states near the conduction band minimum are observed despite the presence of defects detected by STM and STS. As a result, the Fermi level (EF) resides below the conduction band of MoS2. The study also examines the impact of annealing on the contact interface, revealing no interface reaction between Bi and MoS2 up to 300 °C. These findings enhance our understanding of semimetal (Bi) contacts on MoS2, with implications for improving the performance and reliability of electronic devices.

In Situ Active Switching of Bipolar Current Rectification in 2D Semiconductor Vertical Diodes.

Two-dimensional semiconducting transition-metal dichalcogenides (TMDCs) have attracted extensive attention as building blocks of miniaturized electronic and optical devices. However, as the characteristics of TMDC devices are predominately determined by their device structures, the function of TMDC devices is fixed once fabricated, leaving the reconfigurable active device and circuit a challenge. Here, we have demonstrated the current rectification switching in TMDC vertical diodes using a liquid metal (EGaIn) top electrode with a reconfigurable contact area. The rectification switching is closely related to the ultrathin gallium oxide layer on the surface of EGaIn. Under the small contact, with the existence of gallium oxide, photocurrent dominates the electrical transport showing a negative rectification, while as the contact increases, the broken gallium oxide leads to rectification switching to the positive bias direction. Such rectification switching applies to thin TMDC flakes down to 3 nm, benefitting from the soft electrical contact between the TMDC and the EGaIn electrode. Our work shows the new possibility of actively reconfigurable TMDC vertical diodes enabled by the liquid metal electrode and will promote promising applications of flexible and tunable TMDC-based nanoelectronic devices.

Junctionless Electric-Double-Layer MoS2 Field-Effect Transistor with a Sub-5 nm Thick Electrostatically Highly Doped Channel.

Junctionless transistors are suitable for sub-3 nm applications because of their extremely simple structure and high electrical performance, which compensate for short-channel effects. Two-dimensional semiconductor transition-metal dichalcogenide materials, such as MoS2, may also resolve technical and fundamental issues for Si-based technology. Here, we present the first junctionless electric-double-layer field-effect transistor with an electrostatically highly doped 5 nm thick MoS2 channel. A double-gated MoS2 transistor with an ionic-liquid top gate and a conventional bottom gate demonstrated good transfer characteristics with a 104 on-off current ratio, a 70 mV dec-1 subthreshold swing at a 0 V bottom-gate bias, and drain-current versus top-gate-voltage characteristics were shifted left significantly with increasing bottom-gate bias due to an electrostatically increased overall charge carrier concentration in the MoS2 channel. When a bottom-gate bias of 80 V was applied, a shoulder and two clear peak features were identified in the transconductance and its derivative, respectively; this outcome is typical of Si-based junctionless transistors. Furthermore, the decrease in electron mobility induced by a transverse electric field was reduced with increasing bottom-gate bias. Numerical simulations and analytical models were used to support these findings, which clarify the operation of junctionless MoS2 transistors with an electrostatically highly doped channel.

Highly Efficient Experimental Approach to Evaluate Metal to 2D Semiconductor Interfaces in Vertical Diodes with Asymmetric Metal Contacts.

The energy band alignments and associated material properties at the contacts between metal and two-dimensional (2D) semiconducting transition metal dichalcogenide (SCTMD) films determine the important traits in 2D SCTMD-based electronic and optical device applications. In this work, we realize 2D vertical diodes with asymmetric metal-SCTMD contact areas where currents are dominated by the contact-limited charge flows in the transport regimes of Fowler-Nordheim tunneling and Schottky emission. With straightforward current-voltage characteristics, we can accurately evaluate the interface parameters such as Schottky barrier heights and the vertical effective masses of tunneling charges. In particular, the differing contact areas and resultant current rectifications allow us to address specific Schottky barrier locations with respect to the conduction and valence band edges of 2D semiconducting WSe2, WS2, MoSe2, and MoS2, thereby determining whether p-type holes or n-type electrons become the majority charge carriers in the SCTMD devices. We demonstrate that our experimental and analytical approaches can be utilized as a simple but powerful material metrology to qualitatively and quantitatively evaluate various metal-SCTMD contacts.

Direct Optoelectronic Imaging of 2D Semiconductor-3D Metal Buried Interfaces.

The semiconductor-metal junction is one of the most critical factors for high-performance electronic devices. In two-dimensional (2D) semiconductor devices, minimizing the voltage drop at this junction is particularly challenging and important. Despite numerous studies concerning contact resistance in 2D semiconductors, the exact nature of the buried interface under a three-dimensional (3D) metal remains unclear. Herein, we report the direct measurement of electrical and optical responses of 2D semiconductor-metal buried interfaces using a recently developed metal-assisted transfer technique to expose the buried interface, which is then directly investigated using scanning probe techniques. We characterize the spatially varying electronic and optical properties of this buried interface with <20 nm resolution. To be specific, potential, conductance, and photoluminescence at the buried metal/MoS2 interface are correlated as a function of a variety of metal deposition conditions as well as the type of metal contacts. We observe that direct evaporation of Au on MoS2 induces a large strain of ∼5% in the MoS2 which, coupled with charge transfer, leads to degenerate doping of the MoS2 underneath the contact. These factors lead to improvement of contact resistance to record values of 138 kΩ µm, as measured using local conductance probes. This approach was adopted to characterize MoS2-In/Au alloy interfaces, demonstrating contact resistance as low as 63 kΩ µm. Our results highlight that the MoS2/metal interface is sensitive to device fabrication methods and provide a universal strategy to characterize buried contact interfaces involving 2D semiconductors.

Dipole Orientation Shift of Ga2Se2 by Quantum Confinement.

In the family of III-VI monochalcogenides M2X2 (M = gallium, indium; X = sulfur, selenide, etc.), the interlayer interaction and the electronic band edges share the contribution of the same chalcogenide atomic orbits. This makes quantum confinement and interlayer interaction play a subtle role in two-dimensional (2D) monochalcogenides crystals. In this report, we study the direction-resolved photoluminescence of 2D Ga2Se2 at various thicknesses. We observe that the in-plane dipole radiation survives, but out-of-plane dipole radiation fades at 2D limits.

Ultrafast and Sensitive Self-Powered Photodetector Featuring Self-Limited Depletion Region and Fully Depleted Channel with van der Waals Contacts.

Self-powered photodetectors with great potential for implanted medical diagnosis and smart communications have been severely hindered by the difficulty of simultaneously achieving high sensitivity and fast response speed. Here, we report an ultrafast and highly sensitive self-powered photodetector based on two-dimensional (2D) InSe, which is achieved by applying a device architecture design and generating ideal Schottky or ohmic contacts on 2D layered semiconductors, which are difficult to realize in the conventional semiconductors owing to their surface Fermi-level pinning. The as-fabricated InSe photodiode features a maximal lateral self-limited depletion region and a vertical fully depleted channel. It exhibits a high detectivity of 1.26 × 1013 Jones and an ultrafast response speed of ∼200 ns, which breaks the response speed limit of reported self-powered photodetectors based on 2D semiconductors. The high sensitivity is achieved by an ultralow dark current noise generated from the robust van der Waals (vdW) Schottky junction and a high photoresponsivity due to the formation of a maximal lateral self-limited depletion region. The ultrafast response time is dominated by the fast carrier drift driven by a strong built-in electric field in the vertical fully depleted channel. This device architecture can help us to design high-performance photodetectors utilizing vdW layered semiconductors.

Approaching ohmic contact to two-dimensional semiconductors.

Two-dimensional semiconductors have attracted immense research interests owing to their intriguing properties and promising applications in electronic and optoelectronic devices. However, the performance of these devices is drastically hindered by the large Schottky barrier at the electric contact interface, which is hardly tunable due to the Fermi level pinning effect. In this review, we will analyze the root causes of the contact problems for the two-dimensional semiconductor devices and summarize the strategies on the basis of different contact geometries, aiming to lift out the Fermi level pinning effect and achieve the ohmic contact. Moreover, the remarkable improvement of the device performance thanks to these optimized contacts will be emphasized. At the end, the merits and limitations of these strategies will be discussed as well, which potentially gives a guideline for handling the electric contact issues in two-dimensional semiconductors devices.

Robust Piezo-Phototronic Effect in Multilayer γ-InSe for High-Performance Self-Powered Flexible Photodetectors.

The piezo-phototronic effect has been promising as an effective means to improve the performance of two-dimensional (2D) semiconductor based optoelectronic devices. However, the current reported monolayer 2D semiconductors are not regarded as suitable for actual flexible piezotronic photodetectors due to their insufficient optical absorption and mechanical durability, although they possess strong piezoelectricity. In this work, we demonstrate that, unlike 2H-phase transition-metal dichalcogenides, γ-phase InSe with a hexagonal unit cell possesses broken inversion symmetry in all the layer numbers and has a strong second-harmonic generation effect. Moreover, driven by the piezo-phototronic effect, a flexible self-powered photodetector based on multilayer γ-InSe, which can work without any energy supply, is proposed. The device exhibited ultrahigh photon responsivity of 824 mA/W under light illuminations of 400 nm (0.368 mW/cm2). Moreover, the responsivity and response speed of this photodetector were enhanced further by as much as 696% and 1010%, respectively, when a 0.62% uniaxial tensile strain was applied. Our devices exhibit high reliability and stability during a 6 month test time. These significant findings offer a promising pathway to construct high-performance flexible piezo-phototronic photodetectors based on multilayer 2D semiconductors.

Doping-Free Complementary Logic Gates Enabled by Two-Dimensional Polarity-Controllable Transistors.

Atomically thin two-dimensional (2D) materials belonging to transition metal dichalcogenides, due to their physical and electrical properties, are an exceptional vector for the exploration of next-generation semiconductor devices. Among them, due to the possibility of ambipolar conduction, tungsten diselenide (WSe2) provides a platform for the efficient implementation of polarity-controllable transistors. These transistors use an additional gate, named polarity gate, that, due to the electrostatic doping of the Schottky junctions, provides a device-level dynamic control of their polarity, that is, n- or p-type. Here, we experimentally demonstrate a complete doping-free standard cell library realized on WSe2 without the use of either chemical or physical doping. We show a functionally complete family of complementary logic gates (INV, NAND, NOR, 2-input XOR, 3-input XOR, and MAJ) and, due to the reconfigurable capabilities of the single devices, achieve the realization of highly expressive logic gates, such as exclusive-OR (XOR) and majority (MAJ), with fewer transistors than possible in conventional complementary metal-oxide-semiconductor logic. Our work shows a path to enable doping-free low-power electronics on 2D semiconductors, going beyond the concept of unipolar physically doped devices, while suggesting a road to achieve higher computational densities in two-dimensional electronics.

Surface-Enhanced Raman Spectroscopy of Two-Dimensional Tin Diselenide Nanoplates.

Surface-enhanced Raman spectroscopy (SERS) is a powerful spectroscopy technique to detect and characterize molecules at a very low concentration level. The two-dimensional (2D) semi-conductor layered material, tin diselenide (SnSe2), is used as a new substrate for enhancing the Raman signals of adsorbed molecules. Three kinds of molecules-Rhodamine 6G (R6G), crystal violet (CV), and methylene blue (MB)-are used as probe molecules to evaluate the SERS performance of SnSe2. The Raman signals of different molecules can be enhanced by SnSe2 nanoplates (NPs). The distinguishable Raman signal of R6G molecules can be obtained for adsorbent concentrations as low as 10-17 mol/L. Based on a detailed analysis of the bandgap structure and opto-electrical properties of SnSe2 NPs, we discuss the process of charge transfer and the Raman enhancement mechanism of SnSe2 NP. The high Raman sensitivity of SnSe2 NPs is related to the charge transfer between molecules and SnSe2, 2D layered structure, and indirect bandgap of few-layered SnSe2. The research results will help to expand the application of SnSe2 in microanalysis, improve the measurement accuracy of SERS, and possibly find use in optoelectronic device integration.

Charge-Transfer-Induced p-Type Channel in MoS2 Flake Field Effect Transistors.

The two-dimensional transition-metal dichalcogenide semiconductor MoS2 has received extensive attention for decades because of its outstanding electrical and mechanical properties for next-generation devices. One weakness of MoS2, however, is that it shows only n-type conduction, revealing its limitations for homogeneous PN diodes and complementary inverters. Here, we introduce a charge-transfer method to modify the conduction property of MoS2 from n- to p-type. We initially deposited an n-type InGaZnO (IGZO) film on top of the MoS2 flake so that electron charges might be transferred from MoS2 to IGZO during air ambient annealing. As a result, electron charges were depleted in MoS2. Such charge depletion lowered the MoS2 Fermi level, which makes hole conduction favorable in MoS2 when optimum source/drain electrodes with a high work function are selected. Our IGZO-supported MoS2 flake field effect transistors (FETs) clearly display channel-type conversion from n- to p-channel in this way. Under short- and long-annealing conditions, n- and p-channel MoS2 FETs are achieved, respectively, and a low-voltage complementary inverter is demonstrated using both channels in a single MoS2 flake.

Realizing Stable p-Type Transporting in Two-Dimensional WS2 Films.

Two-dimensional (2D) semiconductors have become promising candidates for nanoelectronics applications due to their unique layered structure and rich physical properties. However, the significant lack of reproducible p-type doping methods that can avoid the instability induced by the widely used charge transfer doping method greatly limits the applications of these semiconductors in complementary metal-oxide-semiconductor (CMOS) integrated digital circuits. This work presents a new scheme to realize stable p-type doping for WS2 with excellent layer controllability, wafer-level uniformity, and high reproducibility at the same time. The p-type WS2 was produced by introducing substitutional doping of sulfur with nitrogen atoms during the sulfurization of WOxNy film. Nitrogen atoms acted as acceptors moving the Fermi level of WS2 toward the valance band. Both experimental and theoretical investigations were designed to study the physical properties of the films fabricated. The WS2 based field-effect transistors exhibited a well-defined p-type behavior with a large on/off current ratio of ∼105 and a high hole mobility of ∼18.8 cm2 V-1 s-1. This opens up a promising method to realize stable p-type doping of 2D materials, which is very attractive for future large-scale 2D CMOS device applications.