Ultrathin 2D Photodetectors Utilizing Chemical Vapor Deposition Grown WS₂ With Graphene Electrodes

In this report, graphene (Gr) is used as a 2D electrode and monolayer WS₂ as the active semiconductor in ultrathin photodetector devices. All of the 2D materials are grown by chemical vapor deposition (CVD) and thus pose as a viable route to scalability. The monolayer thickness of both electrode and semiconductor gives these photodetectors ∼2 nm thickness. We show that graphene is different to conventional metal (Au) electrodes due to the finite density of states from the Dirac cones of the valence and conduction bands, which enables the photoresponsivity to be modulated by electrostatic gating and light input control. We demonstrate lateral Gr–WS₂–Gr photodetectors with photoresponsivities reaching 3.5 A/W under illumination power densities of 2.5 × 10⁷ mW/cm². The performance of monolayer WS₂ is compared to bilayer WS₂ in photodetectors and we show that increased photoresponsivity is achieved in the thicker bilayer WS₂ crystals due to increased optical absorption. This approach of incorporating graphene electrodes in lateral TMD based devices provides insights on the contact engineering in 2D optoelectronics, which is crucial for the development of high performing ultrathin photodetector arrays for versatile applications

Utilizing Interlayer Excitons in Bilayer WS₂ for Increased Photovoltaic Response in Ultrathin Graphene Vertical Cross-Bar Photodetecting Tunneling Transistors

Here we study the layer-dependent photoconductivity in Gr/WS₂/Gr vertical stacked tunneling (VST) cross-bar devices made using two-dimensional (2D) materials all grown by chemical vapor deposition. The larger number of devices (>100) enables a statistically robust analysis on the comparative differences in the photovoltaic response of monolayer and bilayer WS₂, which cannot be achieved in small batch devices made using mechanically exfoliated materials. We show a dramatic increase in photovoltaic response for Gr/WS₂(2L)/Gr compared to monolayers because of the long inter- and intralayer exciton lifetimes and the small exciton binding energy (both interlayer and intralayer excitons) of bilayer WS₂ compared with that of monolayer WS₂. Different doping levels and dielectric environments of top and bottom graphene electrodes result in a potential difference across a ∼1 nm vertical device, which gives rise to large electric fields perpendicular to the WS₂ layers that cause band structure modification. Our results show how precise control over layer number in all 2D VST devices dictates the photophysics and performance for photosensing applications

Revealing Strain-Induced Effects in Ultrathin Heterostructures at the Nanoscale

Two-dimensional materials are being increasingly studied, particularly for flexible and wearable technologies because of their inherent thickness and flexibility. Crucially, one aspect where our understanding is still limited is on the effect of mechanical strain, not on individual sheets of materials, but when stacked together as heterostructures in devices. In this paper, we demonstrate the use of Kelvin probe microscopy in capturing the influence of uniaxial tensile strain on the band-structures of graphene and WS₂ (mono- and multilayered) based heterostructures at high resolution. We report a major advance in strain characterization tools through enabling a single-shot capture of strain defined changes in a heterogeneous system at the nanoscale, overcoming the limitations (materials, resolution, and substrate effects) of existing techniques such as optical spectroscopy. Using this technique, we observe that the work-functions of graphene and WS₂ increase as a function of strain, which we attribute to the Fermi level lowering from increased p-doping. We also extract the nature of the interfacial heterojunctions and find that they get strongly modulated from strain. We observe that the strain-enhanced charge transfer with the substrate plays a dominant role, causing the heterostructures to behave differently from two-dimensional materials in their isolated forms

Revealing Defect-State Photoluminescence in Monolayer WS₂ by Cryogenic Laser Processing

Understanding the stability of monolayer transition metal dichalcogenides in atmospheric conditions has important consequences for their handling, life-span, and utilization in applications. We show that cryogenic photoluminescence spectroscopy (PL) is a highly sensitive technique to the detection of oxidation induced degradation of monolayer tungsten disulfide (WS₂) caused by exposure to ambient conditions. Although long-term exposure to atmospheric conditions causes massive degradation from oxidation that is optically visible, short-term exposure produces no obvious changes to the PL or Raman spectra measured at either room temperature or even cryogenic environment. Laser processing was employed to remove the surface adsorbents, which enables the defect states to be detected via cryogenic PL spectroscopy. Thermal cycling to room temperature and back down to 77 K shows the process is reversible. We also monitor the degradation process of WS₂ using this method, which shows that the defect related peak can be observed after one month aging in ambient conditions

Negative Electro-conductance in Suspended 2D WS₂ Nanoscale Devices

We study the <i>in situ</i> electro-conductance in nanoscale electronic devices composed of suspended monolayer WS₂ with metal electrodes inside an aberration-corrected transmission electron microscope. Monitoring the conductance changes when the device is exposed to the electron beam of 80 keV energy reveals a reversible decrease in conductivity with increasing beam current density. The response time of the electro-conductance when exposed to the electron beam is substantially faster than the recovery time when the beam is turned off. We propose a charge trap model that accounts for excitation of electrons into the conduction band and localized trap states from energy supplied by inelastic scattering of incident 80 keV electrons. These results show how monolayer transition metal dichalcogenide 2D semiconductors can be used as transparent direct electron detectors in ultrathin nanoscale devices

Biexciton Formation in Bilayer Tungsten Disulfide

Monolayer transition metal dichalcogenides (TMDs) are direct band gap semiconductors, and their 2D structure results in large binding energies for excitons, trions, and biexcitons. The ability to explore many-body effects in these monolayered structures has made them appealing for future optoelectronic and photonic applications. The band structure changes for bilayer TMDs with increased contributions from indirect transitions, and this has limited similar in-depth studies of biexcitons. Here, we study biexciton emission in bilayer WS₂ grown by chemical vapor deposition as a function of temperature. A biexciton binding energy of 36 ±4 meV is measured in the as-grown bilayer WS₂ containing 0.4% biaxial strain as determined by Raman spectroscopy. The biexciton emission was difficult to detect when the WS₂ was transferred to another substrate to release the stain. Density functional theory calculations show that 0.4% of tensile strain lowers the direct band gap by about 55 meV without significant change to the indirect band gap, which can cause an increase in the quantum yield of direct exciton transitions and the emission from biexcitons formed by two direct gap excitons. We find that the biexciton emission decreases dramatically with increased temperature due to the thermal dissociation, with an activation energy of 26 ± 5 meV. These results show how strain can be used to tune the many-body effects in bilayered TMD materials and extend the photonic applications beyond pure monolayer systems

High-Performance All 2D-Layered Tin Disulfide: Graphene Photodetecting Transistors with Thickness-Controlled Interface Dynamics

Tin disulfide crystals with layered two-dimensional (2D) sheets are grown by chemical vapor deposition using a novel precursor approach and integrated into all 2D transistors with graphene (Gr) electrodes. The Gr:SnS₂:Gr transistors exhibit excellent photodetector response with high detectivity and photoresponsivity. We show that the response of the all 2D photodetectors depends upon charge trapping at the interface and the Schottky barrier modulation. The thickness-dependent SnS₂ measurements in devices reveal a transition from the interface-dominated response for thin crystals to bulklike response for the thicker SnS₂ crystals, showing the sensitivity of devices fabricated using layered materials on the number of layers. These results show that SnS₂ has photosensing performance when combined with Gr electrodes that is comparable to other 2D transition metal dichalcogenides of MoS₂ and WS₂

Doping Graphene Transistors Using Vertical Stacked Monolayer WS₂ Heterostructures Grown by Chemical Vapor Deposition

We study the interactions in graphene/WS₂ two-dimensional (2D) layered vertical heterostructures with variations in the areal coverage of graphene by the WS₂. All 2D materials were grown by chemical vapor deposition and transferred layer by layer. Photoluminescence (PL) spectroscopy of WS₂ on graphene showed PL quenching along with an increase in the ratio of exciton/trion emission, relative to WS₂ on SiO₂ surface, indicating a reduction in the n-type doping levels of WS₂ as well as reduced radiative recombination quantum yield. Electrical measurements of a total of 220 graphene field effect transistors with different WS₂ coverage showed double-Dirac points in the field effect measurements, where one is shifted closer toward the 0 V gate neutrality position due to the WS₂ coverage. Photoirradiation of the WS₂ on graphene region caused further Dirac point shifts, indicative of a reduction in the p-type doping levels of graphene, revealing that the photogenerated excitons in WS₂ are split across the heterostructure by electron transfer from WS₂ to graphene. Kelvin probe microscopy showed that regions of graphene covered with WS₂ had a smaller work function and supports the model of electron transfer from WS₂ to graphene. Our results demonstrate the formation of junctions within a graphene transistor through the spatial tuning of the work function of graphene using these 2D vertical heterostructures

Chemical Vapor Deposition Growth of Two-Dimensional Monolayer Gallium Sulfide Crystals Using Hydrogen Reduction of Ga₂S₃

Two-dimensional gallium sulfide (GaS) crystals are synthesized by a simple and efficient ambient pressure chemical vapor deposition (CVD) method using a single-source precursor of Ga₂S₃. The synthesized GaS structures involve triangular monolayer domains and multilayer flakes with thickness of 1 and 15 nm, respectively. Regions of continuous films of GaS are also achieved with about 0.7 cm² uniform coverage. This is achieved by using hydrogen carrier gas and the horizontally placed SiO₂/Si substrates. Electron microscopy and spectroscopic measurements are used to characteristic the CVD-grown materials. This provides important insights into novel approaches for enlarging the domain size of GaS crystals and understanding of the growth mechanism using this precursor system

Photoluminescence Segmentation within Individual Hexagonal Monolayer Tungsten Disulfide Domains Grown by Chemical Vapor Deposition

We show that hexagonal domains of monolayer tungsten disulfide (WS₂) grown by chemical vapor deposition (CVD) with powder precursors can have discrete segmentation in their photoluminescence (PL) emission intensity, forming symmetric patterns with alternating bright and dark regions. Two-dimensional maps of the PL reveal significant reduction within the segments associated with the longest sides of the hexagonal domains. Analysis of the PL spectra shows differences in the exciton to trion ratio, indicating variations in the exciton recombination dynamics. Monolayers of WS₂ hexagonal islands transferred to new substrates still exhibit this PL segmentation, ruling out local strain in the regions as the dominant cause. High-power laser irradiation causes preferential degradation of the bright segments by sulfur removal, indicating the presence of a more defective region that is higher in oxidative reactivity. Atomic force microscopy (AFM) images of topography and amplitude modes show uniform thickness of the WS₂ domains and no signs of segmentation. However, AFM phase maps do show the same segmentation of the domain as the PL maps and indicate that it is caused by some kind of structural difference that we could not clearly identify. These results provide important insights into the spatially varying properties of these CVD-grown transition metal dichalcogenide materials, which may be important for their effective implementation in fast photo sensors and optical switches