High-quality Monolayer Research Articles

High-performance n-type transistors based on CVD-grown large-domain trilayer WSe2

Atomically thin layered tungsten diselenide (WSe2) has attracted tremendous research attention for its potential applications in next-generation electronics. This article reports the synthesis method of high-quality monolayer to trilayer WSe2 by molten-salt-assisted chemical vapor deposition. With the optimization of different types of molten salts and depths of corundum boat, large trilayer WSe2 films can be grown with domain size up to 80 µm for the first time. A systematic study of the electrical properties of the n-type field-effect transistor has been carried out based on WSe2 with the above three different layer thicknesses. The trilayer WSe2 devices exhibit higher drive current, mobility, on/off ratio, and lower contact resistance than both bilayer and monolayer counterparts. Moreover, short channel transistors using the trilayer WSe2 with a channel length of 230 nm have been fabricated, exhibiting an excellent on/off ratio up to 108 and a high current density of 187 µA/μm. This facile synthesis of high-quality large-area multilayer WSe2 provides a pathway for future high-performance two-dimensional electronic devices.

Stabilization of Chemical-Vapor-Deposition-Grown WS2 Monolayers at Elevated Temperature with Hexagonal Boron Nitride Encapsulation.

Chemical vapor deposition (CVD)-grown flakes of high-quality monolayers of WS2 can be stabilized at elevated temperatures by encapsulation with several layer hexagonal boron nitride (h-BN), but to different degrees in the presence of ambient air, flowing N2, and flowing forming gas (95% N2, 5% H2). The best passivation of WS2 at elevated temperature occurs for h-BN-covered samples with flowing N2 (after heating to 873 K), as judged by optical microscopy and photoluminescence (PL) intensity after a heating/cooling cycle. Stability is worse for uncovered samples, but best with flowing forming gas. PL from trions, in addition to that from excitons, is seen for covered WS2 only for forming gas, during cooling below ∼323 K; the trion has an estimated binding energy of ∼28 meV. It might occur because of doping level changes caused by charge defect generation by H2 molecules diffusing between the h-BN and the SiO2/Si substrate. The decomposition of uncovered WS2 flakes in air suggests a dissociation and chemisorption energy barrier of O2 on the WS2 surface of ∼1.6 eV. Fitting the high-temperature PL intensities in air gives a binding energy of a free exciton of ∼229 meV.

Resolving the intrinsic bandgap and edge effect of BiI3 film epitaxially grown on graphene

Two-dimensional materials with layered structures, appropriate bandgap, and high carrier mobilities have gathered tremendous interests due to their potential applications in optoelectronic and photovoltaic devices. Here, we report the growth of BiI3 thin film with controllable atomic thickness on graphene-terminated 6H–SiC(0001) substrate by molecular beam epitaxy (MBE) method. The growth kinetic processes and crystalline properties of the BiI3 film are studied by scanning tunneling microscopy (STM). The scanning tunneling spectroscopy (STS) reveals a bandgap of 2.8 eV for monolayer BiI3 with a weak dependence on film thickness for few-layer BiI3, which greatly exceeds the previous reported values identified by macroscopic optical measurements. This discrepancy originates from the edge effect of BiI3 that renders the bandgap downshift to 1.5–1.6 eV, as identified by the STS curves and the further confirmed by density functional theory (DFT) calculations. Our work provides a method to fabricate high-quality monolayer BiI3 film and resolves its intrinsic bandgap as well as the edge effect on reduction of bandgap, benefitting not only to fundamental researches but also to nanoelectronic and optoelectronic applications.

Gas-Phase "Prehistory" and Molecular Precursors in Monolayer Metal Dichalcogenides Synthesis: The Case of MoS2.

Two-dimensional MoS2 is one of the most promising materials for nanoelectronics due to its semiconducting nature and plethora of extraordinary properties. The main method for mass production of large-scale, high-quality MoS2 monolayers is chemical vapor deposition (CVD). Yet, the details of the chemistry occurring during the synthesis remain largely unknown, hindering process optimization. Combining ab initio molecular dynamics (AIMD) simulations and first-principles calculations allows us to explore the complete processes of MoS2 monolayer growth at the atomic level. We find that solid MoO3 precursor sublimates forming ringlike molecules, such as Mo3O9, which can later be regarded as gas-phase Mo-carrier reactants, undergoing sulfurization in three main stages: ring opening, chain breaking as the rate-limiting step, and further sulfurization. The fully sulfurized MoS6 molecule emerges as an immediate gas precursor to the crystal growth, as it reacts to join the MoS2-layer edge, with the release of a S4 molecule. Our comprehensive study provides detailed insights into the microscopic reaction mechanisms of MoS2 CVD growth and guidance for optimizing the synthesis parameters for transition metal dichalcogenides.

Tension gradient-driven rapid self-assembly method of large-area colloidal crystal film and its application in multifunctional structural color displays

Liquid-air interface self-assembly (such as the classic L-B method) is the most popular way to form high-quality colloidal crystal monolayers, yet still limited by sophisticated equipment, time-consuming processes and small preparation area. Here, a tension gradient-driven nanoparticle self-assembly method is proposed to realize the high-efficiency and low-cost fabrication of large-area (25 × 18 cm2) colloidal crystal film. The periodic nanoparticle structures composed of various particles with different materials and diameters can be easily obtained in a short time and transferred to various substrates under this self-assembly method. And the preparation area is one to two orders of magnitude higher than the conventional self-assembly method. The simulation results align well with experiments, indicating that the Marangoni effect induced by tension gradient is the main driving force for self-assembly. The influence of various self-assembly parameters is investigated. Inspired by amber, a periodic particle/PDMS/nano-silica particles composite film is further designed to form a large-area durable structural color display. The structural color of the composite film is surprisingly different from that of the periodic particle which was mainly due to the unique semi-coated structure. The composite film has outstanding superhydrophobic and self-cleaning performance with a broad impact on durable structural color displays/sensors, anti-counterfeiting and other aspects.

Suspended graphene on germanium: selective local etching via laser-induced photocorrosion of germanium

The implementation of graphene in nanoelectromechanical systems and electronic applications requires not only techniques to fabricate high-quality monolayers, but also methods to process these layers. Nondestructive processing is especially challenging in the case of fragile suspended graphene membranes. In this work, we present a direct writing method for graphene grown on germanium that yields suspended layers without the need to transfer the graphene layer. To this end, we employ laser-induced photoelectrochemical etching which is highly selective and dissolves only germanium leaving the graphene layer intact. Only a focused continuous wave laser beam and water (or an aqueous solution) are required for the etching to proceed. Raman spectroscopy measurements were performed in-situ to monitor the etching process. These measurements reveal a dramatic increase of the graphene-related Raman bands as the graphene layer detaches from the substrate. This substantial increase indicates that the commonly observed weak Raman signal for graphene on germanium is not an inherent material property but is due to the interaction of the germanium substrate with graphene. Together with the established graphene growth on germanium, the presented direct writing method builds a complete toolbox for graphene membrane-based applications.

Fabrication of Graphene Nanomesh FET Terahertz Detector.

High sensitivity detection of terahertz waves can be achieved with a graphene nanomesh as grating to improve the coupling efficiency of the incident terahertz waves and using a graphene nanostructure energy gap to enhance the excitation of plasmon. Herein, the fabrication process of the FET THz detector based on the rectangular GNM (r-GNM) is designed, and the THz detector is developed, including the CVD growth and the wet-process transfer of high quality monolayer graphene films, preparation of r-GNM by electron-beam lithography and oxygen plasma etching, and the fabrication of the gate electrodes on the Si3N4 dielectric layer. The problem that the conductive metal is easy to peel off during the fabrication process of the GNM THz device is mainly discussed. The photoelectric performance of the detector was tested at room temperature. The experimental results show that the sensitivity of the detector is 2.5 A/W (@ 3 THz) at room temperature.

High-quality remote plasma enhanced atomic layer deposition of aluminum oxide thin films for nanoelectronics applications

Here, we report comprehensive investigations of aluminum oxide (Al2O3) high-κ gate oxides deposited via remote plasma enhanced atomic layer deposition (Re-PEALD) with mesh configuration in a commercial 100 mm ALD reactor. Trimethylaluminum (Al(CH3)3), dioxygen (O2) plasma, and Argon (Ar) are used as the metal precursor, oxidant, and carrier/purge, respectively. The growth rate per cycle and non-uniformity of Al2O3 thin films is analyzed with the variation in duration of (Al(CH3)3) pulse, O2 plasma, post-precursor purge, post-oxidant purge, RF power, and substrate temperature. High-quality monolayer type Al2O3 thin films with a growth rate of ~ 1.1 Å/cycle are achieved for a wide temperature range from ~ 100 °C to ~ 300 °C suitable for various nanoelectronics applications ranging from flexible substrates to low thermal budget and high mobility alternate semiconductor substrates. Further, the Al/Re-PEALD-Al2O3/p-Si, metal-oxide-semiconductor (MOS) structures are investigated for capacitance-voltage, capacitance-frequency, and leakage current-voltage characteristics to demonstrate the quality of Re-PEALD-Al2O3 thin films. The Al/Re-PEALD-Al2O3/p-Si, MOS structures revealed excellent electrical characteristics with ultralow minimum interface trap density (Dit) ~ 9.9 × 109 eV−1cm−2, negative effective oxide charges (Neff) ~ 5.52 × 1012 cm−2, low leakage current density of ~ 4.1 nA/cm2 at −1 V, hysteresis-free, insignificant Vth shift, and trivial frequency dispersion. Moreover, the chemical analysis using XPS depth profiling disclosed that Re-PEALD deposited Al2O3 thin films results in a high-quality gradient Al2O3/SiOx/Si interface rather than an abrupt Al2O3/Si interface, and the oxygen rich thin films due to the oxygen (O2−) interstitials close to the interface are the sources of negative fixed oxide charges in Re-PEALD-Al2O3/Si, system. These results intend to boost the investigations of Re-PEALD Al2O3 ultrathin films for low thermal budget high mobility alternate semiconductor substrates for nanoelectronics applications.

Mechanical exfoliation of large area 2D materials from vdW crystals

Monolayer two-dimensional (2D) materials, such as graphene and transition metal dichalcogenides (TMDCs), provide a versatile platform for exploring novel physical phenomena at the 2D limit, and show great promise for next-generation electronic, optoelectronic, and quantum devices. To overcome the weak van der Waals interaction in the bulk layered crystal and achieve high quality single-crystal monolayers is a crucial task in top-down mechanical exfoliation. Tape exfoliation has long been the dominant approach to obtain single-crystal monolayers with high quality. More recently, there has been a fast development of using metals as an intermediate to enhance monolayer area and exfoliation yield. This review will provide a survey of mechanical exfoliation strategies of tape and metal-assisted exfoliations, particularly for the most popular graphene and TMDC materials. The interfacial interaction and lateral strain between monolayer and other materials such as oxides and metals play a crucial role in monolayer selectivity and yield. The challenges and opportunities will be highlighted for future development of exfoliating procedures to achieve large-area and high-quality 2D material monolayers and artificial stacks.

Synthesis of High-Performance Monolayer Molybdenum Disulfide at Low Temperature.

The large-area synthesis of high-quality MoS2 plays an important role in realizing industrial applications of optoelectronics, nanoelectronics, and flexible devices. However, current techniques for chemical vapor deposition (CVD)-grown MoS2 require a high synthetic temperature and a transfer process, which limits its utilization in device fabrications. Here, the direct synthesis of high-quality monolayer MoS2 with the domain size up to 120µm by metal-organic CVD (MOCVD) at a temperature of 320°C is reported. Owing to the low-substrate temperature, the MOCVD-grown MoS2 exhibits low impurity doping and nearly unstrained properties on the growth substrate, demonstrating enhanced electronic performance with high electron mobility of 68.3 cm2 V-1 s-1 at room temperature. In addition, by tuning the precursor ratio, a better understanding of the MoS2 growth process via a geometric model of the MoS2 flake shape, is developed, which can provide further guidance for the synthesis of 2D materials.

Wafer-Scale Oxygen-Doped MoS2 Monolayer.

Monolayer MoS2 is an emergent 2D semiconductor for next-generation miniaturized and flexible electronics. Although the high-quality monolayer MoS2 is already available at wafer scale, doping of it uniformly remains an unsolved problem. Such doping is of great importance in view of not only tailoring its properties but also facilitating many potential large-scale applications. In this work, the uniform oxygen doping of 2 in wafer-scale monolayer MoS2 (MoS2- x Ox ) with tunable doping levels is realized through an in situ chemical vapor deposition process. Interestingly, ultrafast infrared spectroscopy measurements and first-principles calculations reveal a reduction of bandgaps of monolayer MoS2- x Ox with increased oxygen-doping levels. Field-effect transistors and logic devices are also fabricated based on these wafer-scale MoS2- x Ox monolayers, and excellent electronic performances are achieved, exhibiting promise of such doped MoS2 monolayers.

Salt-assisted growth of monolayer MoS2 for high-performance hysteresis-free field-effect transistor

Atomically thin layered materials such as MoS2 have future versatile applications in low power electronics. Here, we demonstrate the growth of a salt-assisted large scale, high-quality monolayer MoS2 toward the realization of a high-performance hysteresis-free field-effect transistor (FET). Density functional theory calculations are implemented to monitor the effects of the Schottky barrier and metal-induced gap states between our metal electrodes and MoS2 for achieving high carrier transport. The role of absorbed molecules and oxide traps on the hysteresis are studied in detail. For the first time, a hysteresis-free intrinsic transistor behavior is obtained by an amplitude sweep pulse I–V measurement with varying pulse widths. Under this condition, a significant enhancement of the field-effect mobility up to 30 cm2 V−1 s−1 is achieved. Moreover, to correlate these results, a single-pulse time-domain drain current analysis is carried out to unleash the fast and slow transient charge trapping phenomena. Our findings on the hysteresis-free transfer characteristic and high intrinsic field-effect mobility in salt-assisted monolayer MoS2 FETs will be beneficial for future device applications in complex memory, logic, and sensor systems.

Effect of precursor ratio on the morphological and optical properties of CVD-grown monolayer MoS2 nanosheets

Atmosphere pressure chemical vapor deposition (CVD) is one of the most powerful methods of synthesizing high quality and large area MoS2 films with a reasonable cost. In our work, the large-scale and high crystalline quality monolayer MoS2 nanosheets were synthesized on Silicon substrate with a 300 nm oxide layer using MoO3 and S powders as precursors by an atmosphere pressure CVD. The results suggest that the surface morphology, crystalline quality and luminescence of CVD-grown MoS2 nanosheets can be tunable by controlling the precursor ratio (the effective Mo: S ratio). Excessive S-rich atmosphere is favor to synthesize large-size and high crystalline quality monolayer MoS2 nanosheets with sharp corners and straight edges. This study may provide insight into the synthesis of large-scale and high crystalline quality MoS2 films.

Interlayer Coupling and Ultrafast Hot Electron Transfer Dynamics in Metallic VSe2/Graphene van der Waals Heterostructures.

Atomically thin vanadium diselenide (VSe2) is a two-dimensional transition metal dichalcogenide exhibiting attractive properties due to its metallic 1T phase. With the recent development of methods to manufacture high-quality monolayer VSe2 on van der Waals materials, the outstanding properties of VSe2-based heterostructures have been widely studied for diverse applications. Dimensional reduction and interlayer coupling with a van der Waals substrate lead to its distinguishable characteristics from its bulk counterparts. However, only a few fundamental studies have investigated the interlayer coupling effects and hot electron transfer dynamics in VSe2 heterostructures. In this work, we reveal ultrafast and efficient interlayer hot electron transfer and interlayer coupling effects in VSe2/graphene heterostructures. Femtosecond time-resolved reflectivity measurements showed that hot electrons in VSe2 were transferred to graphene within a 100 fs time scale with high efficiency. Besides, coherent acoustic phonon dynamics indicated interlayer coupling in VSe2/graphene heterostructures and efficient thermal energy transfer to three-dimensional substrates. Our results provide valuable insights into the intriguing properties of metallic transition metal dichalcogenide heterostructures and motivate designing optoelectronic and photonic devices with tailored properties.

In Situ Ultrafast and Patterned Growth of Transition Metal Dichalcogenides from Inkjet-Printed Aqueous Precursors.

Chemical vapor deposition (CVD) has been widely used to synthesize high-quality 2D transition-metal dichalcogenides (TMDCs) from different precursors. At present, quantitative control of the precursor with high precision and good repeatability is still challenging. Moreover, the process to synthesize TMDCs with designed patterns is complicated. Here, by using an industrial inkjet-printer, an in situ aqueous precursor with robust usage control at the picogram (10-12 g) level is achieved, and by precisely tuning the inkjet-printing parameters, followed by a rapid heating process, large-area patterned TMDC films with centimeter size and good thickness controllability, as well as heterostructures of the TMDCs, are achieved facilely, and high-quality single-domain monolayer TMDCs with millimeter-size can be easily synthesized within 30 s (corresponding to a growth rate up to 36.4 µm s-1 ). The resulting monolayer MoS2 and MoSe2 exhibits excellent electronic properties with carrier mobility up to 21 and 54 cm2 V-1 s-1 , respectively. The study paves a simple and robust way for the in situ ultrafast and patterned growth of high-quality TMDCs and heterostructures with promising industrialization prospects. Moreover, this ultrafast and green method can be easily used for synthesis of other 2D materials with slight modification.

High electrical conductivity and breakdown current density of individual monolayer Ti3C2Tx MXene flakes

High electrical conductivity and breakdown current density of individual monolayer Ti3C2Tx MXene flakes

Promoting a Weak Coupling of Monolayer MoSe2 Grown on (100)-Faceted Au Foil.

As a two-dimensional semiconductor with many physical properties, including, notably, layer-controlled electronic bandgap and coupled spin-valley degree of freedom, monolayer MoSe2 is a strong candidate material for next-generation opto- and valley-electronic devices. However, due to substrate effects such as lattice mismatch and dielectric screening, preserving the monolayer's intrinsic properties remains challenging. This issue is generally significant for metallic substrates whose active surfaces are commonly utilized to achieve direct chemical or physical vapor growth of the monolayer films. Here, we demonstrate high-temperature-annealed Au foil with well-defined (100) facets as a weakly interacting substrate for atmospheric pressure chemical vapor deposition of highly crystalline monolayer MoSe2. Low-temperature scanning tunneling microscopy/spectroscopy measurements reveal a honeycomb structure of MoSe2 with a quasi-particle bandgap of 1.96 eV, a value comparable with other weakly interacting systems such as MoSe2/graphite. Density functional theory calculations indicate that the Au(100) surface exhibits the preferred energetics to electronically decouple from MoSe2, compared with the (110) and (111) crystal planes. This weak coupling is critical for the easy transfer of monolayers to another host substrate. Our study demonstrates a practical means to produce high-quality monolayers of transition-metal dichalcogenides, viable for both fundamental and application studies.

High-Crystalline Monolayer Transition Metal Dichalcogenides Films for Wafer-Scale Electronics.

Chemical vapor deposition (CVD) using liquid-phase precursors has emerged as a viable technique for synthesizing uniform large-area transition metal dichalcogenide (TMD) thin films. However, the liquid-phase precursor-assisted growth process typically suffers from small-sized grains and unreacted transition metal precursor remainders, resulting in lower-quality TMDs. Moreover, synthesizing large-area TMD films with a monolayer thickness is also quite challenging. Herein, we successfully synthesized high-quality large-area monolayer molybdenum diselenide (MoSe2) with good uniformity via promoter-assisted liquid-phase CVD process using the transition metal-containing precursor homogeneously modified with an alkali metal halide. The formation of a reactive transition metal oxyhalide and reduction of the energy barrier of chalcogenization by the alkali metal promoted the growth rate of the TMDs along the in-plane direction, enabling the full coverage of the monolayer MoSe2 film with negligible few-layer regions. Note that the fully selenized monolayer MoSe2 with high crystallinity exhibited superior electrical transport characteristics compared with those reported in previous works using liquid-phase precursors. We further synthesized various other monolayer TMD films, including molybdenum disulfide, tungsten disulfide, and tungsten diselenide, to demonstrate the broad applicability of the proposed approach.

Growth of Monolayer and Multilayer MoS2 Films by Selection of Growth Mode: Two Pathways via Chemisorption and Physisorption of an Inorganic Molecular Precursor.

We report facile growth methods for high-quality monolayer and multilayer MoS2 films using MoOCl4 as the vapor-phase molecular Mo precursor. Compared to the conventional covalent solid-type Mo precursors, the growth pressure of MoOCl4 can be precisely controlled. This enables the selection of growth mode by adjusting growth pressure, which facilitates the control of the growth behavior as the growth termination at a monolayer or as the continuous growth to a multilayer. In addition, the use of carbon-free precursors eliminates concerns about carbon contamination in the produced MoS2 films. Systematic studies for unveiling the growth mechanism proved two growth modes, which are predominantly the physisorption and chemisorption of MoOCl4. Consequently, the thickness of MoS2 can be controlled by our method as the application demands.

Growth of Very Large MoS2 Single Crystals Using Out-Diffusion Transport and Their Use in Field Effect Transistors

Monolayer molybdenum disulfide (MoS2) is an attractive 2D material with a wide range of potential applications in the field of electronics and optoelectronics. To obtain the best performance, it is very necessary to grow large area single crystals of MoS2 (single domain) to avoid the effects of grain boundaries, but is exceptionally challenging to do this. Here, we report a novel method which we call out-diffusion vapor transport to grow large area single crystal monolayer MoS2 using an otherwise conventional chemical vapor deposition system. In this method, microchannels were created on the boat to significantly limit the region where MoOx vapor can react with S vapor to form crystals. This growth method resulted in triangular monolayer MoS2 single crystals up to ∼640 μm on a side grown on an oxidized silicon substrate, the largest crystals reported to date. Most of these crystals were multilayer at the center. This common feature has been identified in the literature as partially reduced transition metal oxide nucleates a second layer. We also achieved fully monolayer MoS2 single crystals up to ∼450 μm on a side, the largest demonstrated without the MoOx. Fabricated field effect transistors (FET) using MoS2 monolayer crystal as the active layer demonstrate a conventional n-type behavior, room-temperature mobility up to 45.5 cm2 V−1 s−1 and a maximum ON-Current (ION)/OFF-current (IOFF) ratio of 1.8 × 107. Raman and Photoluminescence results indicate that the as-grown large area monolayer crystals have high crystalline quality and uniformity with minimal defects, a finding that is consistent with the high electron mobility. This research work provides a superior technique to grow large-area high-quality single-crystal monolayer MoS2 without resorting to exotic equipment or techniques.