Large-area MoS2 Films Research Articles

(Invited) 2D Semiconductors from Spin-on Molecular Chemistries for Direct Large-Scale Integration

In this talk, I will discuss our recent developments centered on a process to produce fully soluble solutions from a unique molecular chemistry. This enables the creation of wafer-scale monolayers of MoS2, a prominent 2D semiconductor for logic and memory devices. This molecule can be dissolved in common solvents and spin-coated onto various substrates, including crystalline substrates, printed electrodes, and polymers. It can also be integrated into gate-all-around (GAA) 3D transistor structures for logic devices. Our method of rapidly synthesizing large-area MoS2 films, particularly in monolayer form via spin-coating, represents a novelty, as it hasn't been demonstrated previously with a single-source chemistry. This advancement is a significant step toward scalable synthesis of wafer-scale 2D semiconductor thin films, eliminating the need for post-growth wafer transfer techniques, a requirement with films grown by chemical vapor deposition (CVD) methods. Our fabrication process highlights the potential of using a single-source chemical precursor to develop monolayer 2D semiconductors that exhibit commendable transport characteristics and optical properties, which enhance with rising crystallization temperatures. Consequently, it holds promise as a semiconductor for microelectronic transistor channels in both back-end-of-line (BEOL) and front-end-of-line (FEOL) architectures.

Nonconventional Strain Engineering for Uniform Biaxial Tensile Strain in MoS2 Thin Film Transistors.

Strain engineering has been employed as a crucial technique to enhance the electrical properties of semiconductors, especially in Si transistor technologies. Recent theoretical investigations have suggested that strain engineering can also markedly enhance the carrier mobility of two-dimensional (2D) transition-metal dichalcogenides (TMDs). The conventional methods used in strain engineering for Si and other bulk semiconductors are difficult to adapt to ultrathin 2D TMDs. Here, we report a strain engineering approach to apply the biaxial tensile strain to MoS2. Metal-organic chemical vapour deposition (MOCVD)-grown large-area MoS2 films were transferred onto SiO2/Si substrate, followed by the selective removal of the underneath Si. The release of compressive residual stress in the oxide layer induces strain in MoS2 on top of the SiO2 layer. The amount of strain can be precisely controlled by the thickness of oxide stressors. After the transistors were fabricated with strained MoS2 films, the array of strained transistors was transferred onto plastic substrates. This process ensured that the MoS2 channels maintained a consistent tensile strain value across a large area.

Excitonic Rydberg States in a Trilayer to Monolayer H2-Aided CVD-Grown Large-Area MoS2 Film with Excellent UV to Visible Broad Band Photodetection Applications.

The diverse nature of optoelectronic properties of few-layer or monolayer MoS2 is generally dominated by A and B excitons. Occasionally, strong Coulombic interactions within the 2D monolayer led to the creation of hydrogen-like Rydberg states of excitons in MoS2 similar to other 2D monolayers. In this paper, a simple process is used to convert trilayer MoS2 films to a monolayer by introducing H2 gas during chemical vapor deposition. Remarkably, alongside the usual A, B excitons, and A- trion, the appearance of the Rydberg states is evidenced by photoluminescence spectra even at room temperature; also, there is an increase in their areal percentage with an increase in H2 content. The s-type excited Rydberg states up to the fourth order (n = 5) and third order (n = 4) of A and B excitons, respectively, have been probed from the photoluminescence spectra at 93 K. Unprecedentedly, the first-order derivative of room-temperature photocurrent spectrum reveals the Rydberg states concurrently and elaboratively. Furthermore, the large-area MoS2 films exhibit photoresponse in a broad UV to visible region with excellent photosensitivity (∼102) toward both UV and visible lights. Not only does this provide a profound understanding of the excitonic Rydberg states but also highlights the considerable potential of large-area monolayer MoS2 overcoming the difficulty of tiny flake-related 2D device endeavors.

Large-Area MoS2 Films Grown on Sapphire and GaN Substrates by Pulsed Laser Deposition.

In this paper, we present the preparation of few-layer MoS2 films on single-crystal sapphire, as well as on heteroepitaxial GaN templates on sapphire substrates, using the pulsed laser deposition (PLD) technique. Detailed structural and chemical characterization of the films were performed using Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction measurements, and high-resolution transmission electron microscopy. According to X-ray diffraction studies, the films exhibit epitaxial growth, indicating a good in-plane alignment. Furthermore, the films demonstrate uniform thickness on large areas, as confirmed by Raman spectroscopy. The lateral electrical current transport of the MoS2 grown on sapphire was investigated by temperature (T)-dependent sheet resistance and Hall effect measurements, showing a high n-type doping of the semiconducting films (ns from ~1 × 1013 to ~3.4 × 1013 cm-2 from T = 300 K to 500 K), with a donor ionization energy of Ei = 93 ± 8 meV and a mobility decreasing with T. Finally, the vertical current injection across the MoS2/GaN heterojunction was investigated by means of conductive atomic force microscopy, showing the rectifying behavior of the I-V characteristics with a Schottky barrier height of ϕB ≈ 0.36 eV. The obtained results pave the way for the scalable application of PLD-grown MoS2 on GaN in electronics/optoelectronics.

Large area MoS2 thin film growth by direct sulfurization

In this study, we present the growth of monolayer MoS2 (molybdenum disulfide) film. Mo (molybdenum) film was formed on a sapphire substrate through e-beam evaporation, and triangular MoS2 film was grown by direct sulfurization. First, the growth of MoS2 was observed under an optical microscope. The number of MoS2 layers was analyzed by Raman spectrum, atomic force microscope (AFM), and photoluminescence spectroscopy (PL) measurement. Different sapphire substrate regions have different growth conditions of MoS2. The growth of MoS2 is optimized by controlling the amount and location of precursors, adjusting the appropriate growing temperature and time, and establishing proper ventilation. Experimental results show the successful growth of a large-area single-layer MoS2 on a sapphire substrate through direct sulfurization under a suitable environment. The thickness of the MoS2 film determined by AFM measurement is about 0.73 nm. The peak difference between the Raman measurement shift of 386 and 405 cm−1 is 19.1 cm−1, and the peak of PL measurement is about 677 nm, which is converted into energy of 1.83 eV, which is the size of the direct energy gap of the MoS2 thin film. The results verify the distribution of the number of grown layers. Based on the observation of the optical microscope (OM) images, MoS2 continuously grows from a single layer of discretely distributed triangular single-crystal grains into a single-layer large-area MoS2 film. This work provides a reference for growing MoS2 in a large area. We expect to apply this structure to various heterojunctions, sensors, solar cells, and thin-film transistors.

Oxygen-assisted growth of monolayer MoS2 films on graphene by chemical vapor deposition

MoS2/graphene heterojunctions have a great potential for optoelectronic applications. Here, we demonstrate the oxygen (O2) assisted growth of large-area monolayer MoS2 films on graphene using chemical vapor deposition (CVD) technique. The introduction of O2 has greatly improved the growth environment of MoS2 domains as well as increased the grain size of MoS2 from submicron to micron range. Spectroscopic results show that a monolayer of MoS2 with high crystal quality has been deposited on the graphene. Effective charge transfer is observed in MoS2/graphene heterojunctions. MoS2 is doped with different concentrations of O2 in situ by optimizing its flow rates. The photodetector prepared by MoS2/graphene film has a good response to light. Due to the effective photoresponse of synthesized heterojunctions, these would be useful in various applications in the optoelectronic thin films and devices.

Vertical MoS2 transistors with sub-1-nm gate lengths.

Ultra-scaled transistors are of interest in the development of next-generation electronic devices1-3. Although atomically thin molybdenum disulfide (MoS2) transistors have been reported4, the fabrication of devices with gate lengths below 1 nm has been challenging5. Here we demonstrate side-wall MoS2 transistors with an atomically thin channel and a physicalgate length of sub-1 nm using the edge of a graphene layer as the gate electrode. The approach uses large-area graphene and MoS2 films grown by chemical vapour deposition for the fabrication of side-wall transistors on a 2-inch wafer. These devices have On/Off ratios up to 1.02 × 105 and subthreshold swing values down to 117 mV dec-1. Simulation results indicate that the MoS2 side-wall effective channel length approaches 0.34 nm in the On state and 4.54 nm in the Off state. This work can promote Moore's law of the scaling down of transistors for next-generation electronics.

MoS2 hybrid integrated micro-ring resonator phase shifter based on a silicon nitride platform

We demonstrate a low-power, compact micro-ring phase shifter based on hybrid integration with atomically thin two-dimensional layered materials, and experimentally establish a low-loss silicon nitride platform. Using a wet transfer method, a large-area few-layer MoS2 film is hybrid integrated with a micro-ring phase shifter, leading to a tuning efficiency of 5.8 pm V-1 at a center wavelength of 1545.294 nm and a half-wave-voltage-length product as low as 0.09 V cm. Our device is designed to provide a hybrid-integration-based active phase modulation scheme for integrated optical communication networks with large-cross-section silicon nitride waveguides.

Fabrication of Large-Area Molybdenum Disulfide Device Arrays Using Graphene/Ti Contacts.

Two-dimensional (2D) molybdenum disulfide (MoS2) is the most mature material in 2D material fields owing to its relatively high mobility and scalability. Such noticeable properties enable it to realize practical electronic and optoelectronic applications. However, contact engineering for large-area MoS2 films has not yet been established, although contact property is directly associated to the device performance. Herein, we introduce graphene-interlayered Ti contacts (graphene/Ti) into large-area MoS2 device arrays using a wet-transfer method. We achieve MoS2 devices with superior electrical and photoelectrical properties using graphene/Ti contacts, with a field-effect mobility of 18.3 cm2/V∙s, on/off current ratio of 3 × 107, responsivity of 850 A/W, and detectivity of 2 × 1012 Jones. This outstanding performance is attributable to a reduction in the Schottky barrier height of the resultant devices, which arises from the decreased work function of graphene induced by the charge transfer from Ti. Our research offers a direction toward large-scale electronic and optoelectronic applications based on 2D materials.

Sub-10 fs Intervalley Exciton Coupling in Monolayer MoS2 Revealed by Helicity-Resolved Two-Dimensional Electronic Spectroscopy.

The valley pseudospin at the K and K' high-symmetry points in monolayer transition metal dichalcogenides (TMDs) has potential as an optically addressable degree of freedom in next-generation optoelectronics. However, intervalley scattering and relaxation of charge carriers leads to valley depolarization and limits practical applications. In addition, enhanced Coulomb interactions lead to pronounced excitonic effects that dominate the optical response and initial valley depolarization dynamics but complicate the interpretation of ultrafast spectroscopic experiments at short time delays. Employing broadband helicity-resolved two-dimensional electronic spectroscopy (2DES), we observe ultrafast (∼10 fs) intervalley coupling between all A and B valley exciton states that results in a complete breakdown of the valley index in large-area monolayer MoS2 films. These couplings and subsequent dynamics exhibit minimal excitation fluence or temperature dependence and are robust toward changes in sample grain size and inherent strain. Our observations strongly suggest that this direct intervalley coupling on the time scale of optical excitation is an inherent property of large-area MoS2 distinct from dynamic carrier or exciton scattering, phonon-driven processes, and multiexciton effects. This ultrafast intervalley coupling poses a fundamental challenge for exciton-based valleytronics in monolayer TMDs and must be overcome to fully realize large-area valleytronic devices.

Measurement of direct and indirect bandgaps in synthetic ultrathin MoS2 and WS2 films from photoconductivity spectra

Exploring the thickness-dependent electronic properties of ultrathin transition metal dichalcogenides is crucial for novel optoelectronic devices. Particularly important is experimental information regarding the bandgap width. This information is scarce and often inconsistent among the several measurement techniques that were employed for this task, such as optical absorption, scanning tunneling spectroscopy, and photoconductivity. Here, we present photoconductivity measurements in large-area synthetic MoS2 and WS2 films (one to five monolayers and the bulk crystal) grown on insulating layers (SiO2, Al2O3, or HfO2). The excitonic peaks of MoS2 and WS2 were detected in both the photocapacitor and traditional in-plane geometries. Their contribution to the photoconductivity is explained by the electric field-assisted dissociation mechanism. We have separated the excitonic and free carrier components in the photocurrent spectra and extracted the direct and indirect bandgaps using the Tauc plot, revealing their dependencies on the number of monolayers.

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.

Utilizing complex oxide substrates to control carrier concentration in large-area monolayer MoS2 films

Bandgap engineering is central to the design of heterojunction devices. For heterojunctions involving monolayer-thick materials like MoS2, the carrier concentration of the atomically thin film can vary significantly depending on the amount of charge transfer between MoS2 and the substrate. This makes substrates with a range of charge neutrality levels—as is the case for complex oxide substrates—a powerful addition to electrostatic gating or chemical doping to control the doping of overlying MoS2 layers. We demonstrate this approach by growing monolayer MoS2 on perovskite (SrTiO3 and LaAlO3), spinel (MgAl2O4), and SiO2 substrates with multi-inch uniformity. The as-grown MoS2 films on these substrates exhibit a controlled, reproducible, and uniform carrier concentration ranging from (1–4) ×1013 cm−2, depending on the oxide substrate employed. The observed carrier concentrations are further confirmed by our density-functional theory calculations based on ab initio mismatched interface theory (MINT). This approach is relevant to large-scale heterostructures involving monolayer-thick materials in which it is desired to precisely control carrier concentrations for applications.

MoS2-on-AlN Enables High-Performance MoS2 Field-Effect Transistors through Strain Engineering.

Molybdenum disulfide (MoS2) has substantial application prospects in the field of electronic devices. The fabrication of devices of excellent quality based on MoS2 films is an important research direction. In this study, based on the atomic layer deposition technique, large-area MoS2 films were grown, and top-gate MoS2-based field-effect transistor arrays were fabricated on four substrates (AlN, GaN, sapphire, and SiO2). It was found that the interface defects that were introduced by lattice mismatch and roughness of the growth substrate could cause an exponential (102) drop in mobility. Because of the small lattice mismatch and excellent surface quality, transistors on the AlN substrate have shown an enhanced mobility (10.45 cm2 V-1 s-1) compared to transistors on the other substrates. This study proves that the AlN substrate is a superior substrate for large-area and high-performance MoS2 film synthesis. This result can also be applied in higher-level microelectronic systems, such as in digital logic circuit design.

Synthesis of large-area MoS2 films by plasma-enhanced chemical film conversion of solution-processed ammonium tetrathiomolybdate

The synthesis of large-area molybdenum disulfide (MoS2) films is desired for many emerging electronic and optical applications. A typical approach is to deposit films from vapor-phase precursors either by thermal- or plasma-activated chemistry. Here, we show that MoS2 films exhibiting excellent crystallinity and smooth surfaces are produced by plasma conversion of solution-deposited precursor films. Films containing a single-source precursor for MoS2, ammonium tetrathiomolybdate, were spin coated and converted by an atmospheric-pressure dielectric barrier discharge with substrate heating at 500 °C. X-ray diffraction and micro-Raman spectroscopy show that the plasma is necessary to successfully convert the precursor to MoS2. Further enhancements in the crystallinity and surface roughness were obtained by annealing the films, as revealed by high-resolution transmission electron microscopy and atomic force microscopy (AFM). Insights into the role of the plasma were provided by AFM characterization and a “plasma-trigger” experiment, which suggest that a nanocone surface morphology facilitates the growth of the films.

Active-matrix monolithic gas sensor array based on MoS2 thin-film transistors

Highly sensitive and system integrable gas sensors play a significant role in industry and daily life, and MoS2 has emerged as one of the most promising two-dimensional nanomaterials for gas sensor technology. In this study, we demonstrate a scalable and monolithically integrated active-matrix gas sensor array based on large-area bilayer MoS2 films synthesized via two-successive steps: radio-frequency magnetron sputtering and thermal sulfurization. The fabricated thin-film transistors exhibit consistent electrical performance over a few centimeters area and resulting gas sensors detect NO2 with ultra-high sensitivity across a wide detection range, from 1 to 256 ppm. This is due to the abundant grain boundaries of the sputtered MoS2 channel, which perform as active sites for absorption of NO2 gas molecules. The demonstrated active-matrix gas sensor arrays display good switching capabilities and are anticipated to be readily integrated with additional circuitry for different gas sensing and monitoring applications.

Influence of precursor thin-film quality on the structural properties of large-area MoS2 films grown by sulfurization of MoO3 on c-sapphire

In recent years, molybdenum disulfide (MoS2) has been investigated due to its unique electronic, optical, and mechanical properties with a variety of applications. Sulfurization of pre-deposited MoO3 layers is one of the methods of the preparation of large-area MoS2 thin films. The MoO3 layers have been grown on c-sapphire substrates, using two different techniques (rf sputtering, pulsed laser deposition). The films were subsequently annealed in vapors of sulfur at high temperatures what converted them to MoS2 films. The quality of MoS2 is strongly influenced by the properties of the precursor MoO3 layers. The pre-deposited MoO3, as well as the sulfurized MoS2, have been characterized by several techniques including Raman, Rutherford backscattering spectroscopy, atomic force microscopy, scanning electron microscopy, and X-ray diffraction. Here we compare two types of MoS2 films prepared from different MoO3 layers to determine the most suitable MoO3 layer properties providing good quality MoS2 films for future applications.

Large-Area Electrodeposition of Few-Layer MoS2 on Graphene for 2D Material Heterostructures.

Heterostructures involving two-dimensional (2D) transition metal dichalcogenides and other materials such as graphene have a strong potential to be the fundamental building block of many electronic and optoelectronic applications. The integration and scalable fabrication of such heterostructures are of the essence in unleashing the potential of these materials in new technologies. For the first time, we demonstrate the growth of few-layer MoS2 films on graphene via nonaqueous electrodeposition. Through methods such as scanning and transmission electron microscopy, atomic force microscopy, Raman spectroscopy, energy- and wavelength-dispersive X-ray spectroscopies, and X-ray photoelectron spectroscopy, we show that this deposition method can produce large-area MoS2 films with high quality and uniformity over graphene. We reveal the potential of these heterostructures by measuring the photoinduced current through the film. These results pave the way toward developing the electrodeposition method for the large-scale growth of heterostructures consisting of varying 2D materials for many applications.

Surface Coverage Dependence of Spin-to-Charge Current across Pt/MoS2/Y3Fe5O12 Layers via Longitudinal Spin Seebeck Effect

The voltage induced by the inverse spin Hall effect (ISHE) is affected by several factors, including the spin Hall angle of the normal metal (NM), the quality and magnetic properties of the ferromagnetic material (FM), and the interface conditions between the NM and FM bilayers in longitudinal spin Seebeck effect (LSSE) measurement. Specifically, the interface conditions in NM/FM systems via LSSE devices play a crucial role in determining the efficiency of spin current injection into the NM layer. In this letter, we report a new approach to controlling the efficiency of spin current injection into a Pt layer across a Pt/Y3Fe5O12 (YIG) interface by surface coverage of the intermediate layer. A continuous, large-area multilayer molybdenum dichalcogenide (MoS2) thin film grown by chemical vapor deposition is inserted between the Pt and YIG layers in the LSSE configuration. We found that, when the large-area multilayer MoS2 film was present, the measured ISHE-induced voltage and theoretically calculated spin current in the Pt/MoS2/YIG trilayer increased by ∼510% and 470%, respectively, compared to those of a Pt/YIG bilayer. The induced voltage and spin current were very sensitive to the surface conductance, which was affected by the surface coverage of the multilayer MoS2 films in the LSSE measurement. Furthermore, the theoretically calculated spin current and spin mixing conductance in the trilayer geometry are in qualitatively good agreement with the experimental observations. These measurements enable us to explain the effect of the interface conditions on the spin Seebeck effect in spin transport.

Homogeneous dual-gate MoS2 field-effect transistors integrated by atomic layer deposition-based film synthesis

Various synthetic approaches have been proposed and studied to grow high-quality two-dimensional (2D) transition metal dichalcogenides (TMDCs) thin films. However, most of current methods suffer from intrinsic material defects or technical limitations. Here, in this paper, large-area few-layer MoS2 thin films have been prepared on SiO2/Si substrate through sulfurizing pre-deposited MoO3 film by atomic layer deposition (ALD). Good film uniformity, crystallinity and stoichiometry have been successfully achieved. The film thickness can be precisely controlled by adjusting the ALD cycle numbers during MoO3 deposition. Field-effect transistor (FET) arrays have been further fabricated based on the large-area MoS2 film. Both back-gate and top-gate geometries have been applied and have shown excellent reproducibility in electrical performance with average electron mobility of 1.71 cm2 V−1 s−1 and 0.31 cm2 V−1 s−1 for the back-gate and top-gate FETs, respectively. Our results have enabled a promising pathway with such thickness-controlled TMD film and homogeneous FET devices towards future low-dimensional nanoelectronics applications.