An official website of the United States government
ABSTRACT The synthesis of two‐dimensional transition metal dichalcogenide (2D‐TMD) materials gives rise to inherent defects, specifically chalcogen vacancies, due to thermodynamic equilibrium. Techniques such as chemical vapor deposition (CVD), metal‐organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), flux growth method, and mechanical exfoliation produce large‐scale, uniform 2D TMD films, either in bulk or monolayers. However, defects on the film surface impact its quality, and it is necessary to measure defect density. The phonon confinement model indicates that the first‐order Raman band frequency shift depends on defect density. Monolayer Molybdenum disulfide (MoS2) exhibits three phonon dispersions at the Brillouin zone edge (M point): out‐of‐plane optical phonon vibration (ZO), in‐plane longitudinal optical phonon vibration (LO), and in‐plane transverse optical phonon vibration (TO). The LO and ZO modes overlap with Raman in‐plane vibration (𝐸12g) and Raman out‐of‐plane vibration (𝐴1g), respectively, causing peak broadening. In the presence of defects, the Raman 𝐸12gvibration energy decreases due to a reduced restoring force constant. The Raman 𝐴1gvibration trend is random, influenced by both restoring force constant and mass. The study introduces a quantitative defect measurement technique for CVD‐grown monolayer MoS2using Raman 𝐸12gmode, employing sequential data processing algorithms to reveal defect density on the film surface.
more »
« less
Accelerating Optimal Synthesis of Atomically Thin MoS 2 : A Constrained Bayesian Optimization Guided Brachistochrone Approach
Abstract A machine learning (ML) guided approach is presented for the accelerated optimization of chemical vapor deposition (CVD) synthesis of 2D materials toward the highest quality, starting from low‐quality or unsuccessful synthesis conditions. Using 26 sets of these synthesis conditions as the initial training dataset, our method systematically guides experimental synthesis towards optoelectronic‐grade monolayer MoS2flakes. A‐exciton linewidth (σA) as narrow as 38 meV could be achieved in 2D MoS2flakes after only an additional 35 trials (reflecting 15% of the full factorial design dataset for training purposes). In practical terms, this reflects a decrease of the possible experimental time to optimize the parameters from up to one year to about two months. This remarkable efficiency was achieved by formulating a constrained sequencing optimization problem solved via a combination of constraint learning and Bayesian Optimization with the narrowness of σAas the single target metric. By employing graph‐based semi‐supervised learning with data acquired through a multi‐criteria sampling method, the constraint model effectively delineates and refines the feasible design space for monolayer flake production. Additionally, the Gaussian Process regression effectively captures the relationships between synthesis parameters and outcomes, offering high predictive capability along with a measure of prediction uncertainty. This method is scalable to a higher number of synthesis parameters and target metrics and is transferrable to other materials and types of reactors. This study envisions that this method will be fundamental for CVD and similar techniques in the future.
more »
« less
- PAR ID:
- 10549491
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials Technologies
- ISSN:
- 2365-709X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract 2D layered semiconductors have attracted considerable attention for beyond‐Si complementary metal‐oxide‐semiconductor (CMOS) technologies. They can be prepared into ultrathin channel materials toward ultrascaled device architectures, including double‐gate field‐effect‐transistors (DGFETs). This work presents an experimental analysis of DGFETs constructed from chemical vapor deposition (CVD)‐grown monolayer (1L) molybdenum disulfide (MoS2) with atomic layer deposition (ALD) of hafnium oxide (HfO2) high‐k gate dielectrics (top and bottom). This extends beyond previous studies of DGFETs based mostly on exfoliated (few‐nm thick) MoS2flakes, and advances toward large‐area wafer‐scale processing. Here, significant improvements in performance are obtained with DGFETs (i.e., improvements in ON/OFF ratio, ON‐state current, sub‐threshold swing, etc.) compared to single top‐gate FETs. In addition to multi‐gate device architectures (e.g., DGFETs), the scaling of the equivalent oxide thickness (EOT) is crucial toward improved electrostatics required for next‐generation transistors. However, the impact of EOT scaling on the characteristics of CVD‐grown MoS2DGFETs remains largely unexplored. Thus, this work studies the impact of EOT scaling on subthreshold swing (SS) and gate hysteresis using current–voltage (I–V) measurements with varying sweep rates. The experimental analysis and results elucidate the basic mechanisms responsible for improvements in CVD‐grown 1L‐MoS2DGFETs compared to standard top‐gate FETs.more » « less
-
Abstract Chemical vapor deposition (CVD)-grown monolayer (ML) molybdenum disulfide (MoS 2 ) is a promising material for next-generation integrated electronic systems due to its capability of high-throughput synthesis and compatibility with wafer-scale fabrication. Several studies have described the importance of Schottky barriers in analyzing the transport properties and electrical characteristics of MoS 2 field-effect-transistors (FETs) with metal contacts. However, the analysis is typically limited to single devices constructed from exfoliated flakes and should be verified for large-area fabrication methods. In this paper, CVD-grown ML MoS 2 was utilized to fabricate large-area (1 cm × 1 cm) FET arrays. Two different types of metal contacts (i.e. Cr/Au and Ti/Au) were used to analyze the temperature-dependent electrical characteristics of ML MoS 2 FETs and their corresponding Schottky barrier characteristics. Statistical analysis provides new insight about the properties of metal contacts on CVD-grown MoS 2 compared to exfoliated samples. Reduced Schottky barrier heights (SBH) are obtained compared to exfoliated flakes, attributed to a defect-induced enhancement in metallization of CVD-grown samples. Moreover, the dependence of SBH on metal work function indicates a reduction in Fermi level pinning compared to exfoliated flakes, moving towards the Schottky–Mott limit. Optical characterization reveals higher defect concentrations in CVD-grown samples supporting a defect-induced metallization enhancement effect consistent with the electrical SBH experiments.more » « less
-
AbstractThe exotic properties of 2D materials made them ideal candidates for applications in quantum computing, flexible electronics, and energy technologies. A major barrier to their adaptation for industrial applications is their controllable and reproducible growth at a large scale. A significant effort has been devoted to the chemical vapor deposition (CVD) growth of wafer-scale highly crystalline monolayer materials through exhaustive trial-and-error experimentations. However, major challenges remain as the final morphology and growth quality of the 2D materials may significantly change upon subtle variation in growth conditions. Here, we introduced a multiscale/multiphysics model based on coupling continuum fluid mechanics and phase-field models for CVD growth of 2D materials. It connects the macroscale experimentally controllable parameters, such as inlet velocity and temperature, and mesoscale growth parameters such as surface diffusion and deposition rates, to morphology of the as-grown 2D materials. We considered WSe2as our model material and established a relationship between the macroscale growth parameters and the growth coverage. Our model can guide the CVD growth of monolayer materials and paves the way to their synthesis-by-design. Graphic abstractmore » « less
-
Abstract 2D materials have been of considerable interest as new materials for device applications. Non‐volatile resistive switching applications of MoS2and WS2have been previously demonstrated; however, these applications are dramatically limited by high temperatures and extended times needed for the large‐area synthesis of 2D materials on crystalline substrates. The experimental results demonstrate a one‐step sulfurization method to synthesize MoS2and WS2at 550 °C in 15 min on sapphire wafers. Furthermore, a large area transfer of the synthesized thin films to SiO2/Si substrates is achieved. Following this, MoS2and WS2memristors are fabricated that exhibit stable non‐volatile switching and a satisfactory large on/off current ratio (103–105) with good uniformity. Tuning the sulfurization parameters (temperature and metal precursor thickness) is found to be a straightforward and effective strategy to improve the performance of the memristors. The demonstration of large‐scale MoS2and WS2memristors with a one‐step low‐temperature sulfurization method with simple strategy to tuning can lead to potential applications such as flexible memory and neuromorphic computing.more » « less
