Nanopatterning and Electrical Tuning of MoS2 Layers with a Subnanometer Helium Ion Beam.

We report subnanometer modification enabled by an ultrafine helium ion beam. By adjusting ion dose and the beam profile, structural defects were controllably introduced in a few-layer molybdenum disulfide (MoS2) sample and its stoichiometry was modified by preferential sputtering of sulfur at a few-nanometer scale. Localized tuning of the resistivity of MoS2 was demonstrated and semiconducting, metallic-like, or insulating material was obtained by irradiation with different doses of He(+). Amorphous MoSx with metallic behavior has been demonstrated for the first time. Fabrication of MoS2 nanostructures with 7 nm dimensions and pristine crystal structure was also achieved. The damage at the edges of these nanostructures was typically confined to within 1 nm. Nanoribbons with widths as small as 1 nm were reproducibly fabricated. This nanoscale modification technique is a generalized approach that can be applied to various two-dimensional (2D) materials to produce a new range of 2D metamaterials.

Miniaturized spectrometer with intrinsic long-term image memory.

Miniaturized spectrometers have great potential for use in portable optoelectronics and wearable sensors. However, current strategies for miniaturization rely on von Neumann architectures, which separate the spectral sensing, storage, and processing modules spatially, resulting in high energy consumption and limited processing speeds due to the storage-wall problem. Here, we present a miniaturized spectrometer that utilizes a single SnS2/ReSe2 van der Waals heterostructure, providing photodetection, spectrum reconstruction, spectral imaging, long-term image memory, and signal processing capabilities. Interface trap states are found to induce a gate-tunable and wavelength-dependent photogating effect and a non-volatile optoelectronic memory effect. Our approach achieves a footprint of 19 µm, a bandwidth from 400 to 800 nm, a spectral resolution of 5 nm, and a > 104 s long-term image memory. Our single-detector computational spectrometer represents a path beyond von Neumann architectures.

Enhanced NO2 Sensitivity of Vertically Stacked van der Waals Heterostructure Gas Sensor and Its Remarkable Electric and Mechanical Tunability.

Nanodevices based on van der Waals heterostructures have been predicted, and shown, to have unprecedented operational principles and functionalities that hold promise for highly sensitive and selective gas sensors with rapid response times and minimal power consumption. In this study, we fabricated gas sensors based on vertical MoS2/WS2 van der Waals heterostructures and investigated their gas sensing capabilities. Compared with individual MoS2 or WS2 gas sensors, the MoS2/WS2 van der Waals heterostructure gas sensors are shown to have enhanced sensitivity, faster response times, rapid recovery, and a notable selectivity, especially toward NO2. In combination with a theoretical model, we show that it is important to take into account created trapped states (flat bands) induced by the adsorption of gas molecules, which capture charges and alter the inherent built-in potential of van der Waals heterostructure gas sensors. Additionally, we note that the performance of these MoS2/WS2 heterostructure gas sensors could be further enhanced using electrical gating and mechanical strain. Our findings highlight the importance of understanding the effects of altered built-in potentials arising from gas molecule adsorption induced flat bands, thus offering a way to enhance the gas sensing performance of van der Waals heterostructure gas sensors.

Field Effect Transistor Gas Sensors Based on Mechanically Exfoliated Van der Waals Materials.

The high surface-to-volume ratio and flatness of mechanically exfoliated van der Waals (vdW) layered materials make them an ideal platform to investigate the Langmuir absorption model. In this work, we fabricated field effect transistor gas sensors, based on a variety of mechanically exfoliated vdW materials, and investigated their electrical field-dependent gas sensing properties. The good agreement between the experimentally extracted intrinsic parameters, such as equilibrium constant and adsorption energy, and theoretically predicted values suggests validity of the Langmuir absorption model for vdW materials. Moreover, we show that the device sensing behavior depends crucially on the availability of carriers, and giant sensitivities and strong selectivity can be achieved at the sensitivity singularity. Finally, we demonstrate that such features provide a fingerprint for different gases to quickly detect and differentiate between low concentrations of mixed hazardous gases using sensor arrays.

Light-Tunable Polarity and Erasable Physisorption-Induced Memory Effect in Vertically Stacked InSe/SnS2 Self-Powered Photodetector.

van der Waals heterojunctions with tunable polarity are being actively explored for more Moore and more-than-Moore device applications, as they can greatly simplify circuit design. However, inadequate control over the multifunctional operational states is still a challenge in their development. Here, we show that a vertically stacked InSe/SnS2 van der Waals heterojunction exhibits type-II band alignment, and its polarity can be tuned by an external electric field and by the wavelength and intensity of an illuminated light source. Moreover, such SnS2/InSe diodes are self-powered broadband photodetectors with good performance. The self-powered performance can be further enhanced significantly with gas adsorption, and the device can be quickly restored to the state before gas injection using a gate voltage pulse. Our results suggest a way to achieve and design multiple functions in a single device with multifield coupling of light, electrical field, gas, or other external stimulants.

Synthesis and characterisation of thin-film platinum disulfide and platinum sulfide.

Group-10 transition metal dichalcogenides (TMDs) are rising in prominence within the highly innovative field of 2D materials. While PtS2 has been investigated for potential electronic applications, due to its high charge-carrier mobility and strongly layer-dependent bandgap, it has proven to be one of the more difficult TMDs to synthesise. In contrast to most TMDs, Pt has a significantly more stable monosulfide, the non-layered PtS. The existence of two stable platinum sulfides, sometimes within the same sample, has resulted in much confusion between the materials in the literature. Neither of these Pt sulfides have been thoroughly characterised as-of-yet. Here we utilise time-efficient, scalable methods to synthesise high-quality thin films of both Pt sulfides on a variety of substrates. The competing nature of the sulfides and limited thermal stability of these materials is demonstrated. We report peak-fitted X-ray photoelectron spectra, and Raman spectra using a variety of laser wavelengths, for both materials. This systematic characterisation provides a guide to differentiate between the sulfides using relatively simple methods which is essential to enable future work on these interesting materials.

Graphene/SnS2 van der Waals Photodetector with High Photoresponsivity and High Photodetectivity for Broadband 365-2240 nm Detection.

The fabrication of graphene/SnS2 van der Waals photodetectors and their photoelectrical properties are systematically investigated. It was found that a dry transferred graphene/SnS2 van der Waals heterostructure had a broadband sensing range from ultraviolet (365 nm) to near-infrared (2.24 µm) and respective improved responsivities and photodetectivities of 7.7 × 103 A/W and 8.9 × 1013 jones at 470 nm and 2 A/W and 1.8 × 1010 jones at 1064 nm. Moreover, positive and negative photoconductance effects were observed when the photodetectors were illuminated by photon sources with energies greater and smaller than the bandgap of SnS2, respectively. The photoresponsivity (R) versus incident power density (P) follows the empirical law R ∝ Pinß, with ß > -1 for positive photoconductance effects and ß < -1 for negative photoconductance effects. On the basis of the Fowler-Nordheim tunneling model and a Poisson and drift-diffusion simulation, we show quantitatively that the barrier height and barrier width of the heterostructure photodetector could be controlled by a laser and an external electrical field through a photogating effect generated by carriers trapped at the interface, which could be used to tune the separation and transport of photogenerated carriers. Our results may be useful for the design of high performance van der Waals heterojunction photodetectors.

Giant gauge factor of Van der Waals material based strain sensors.

There is an emergent demand for high-flexibility, high-sensitivity and low-power strain gauges capable of sensing small deformations and vibrations in extreme conditions. Enhancing the gauge factor remains one of the greatest challenges for strain sensors. This is typically limited to below 300 and set when the sensor is fabricated. We report a strategy to tune and enhance the gauge factor of strain sensors based on Van der Waals materials by tuning the carrier mobility and concentration through an interplay of piezoelectric and photoelectric effects. For a SnS2 sensor we report a gauge factor up to 3933, and the ability to tune it over a large range, from 23 to 3933. Results from SnS2, GaSe, GeSe, monolayer WSe2, and monolayer MoSe2 sensors suggest that this is a universal phenomenon for Van der Waals semiconductors. We also provide proof of concept demonstrations by detecting vibrations caused by sound and capturing body movements.

Electronic and structural characterisation of polycrystalline platinum disulfide thin films.

We employ a combination of scanning tunnelling microscopy (STM) and scanning tunnelling spectroscopy (STS) to investigate the properties of layered PtS2, synthesised via thermally assisted conversion (TAC) of a metallic Pt thin film. STM measurements reveal the 1T crystal structure of PtS2, and the lattice constant is determined to be 3.58 ± 0.03 Å. STS allowed the electronic structure of individual PtS2 crystallites to be directly probed and a bandgap of ∼1.03 eV was determined for a 3.8 nm thick flake at liquid nitrogen temperature. These findings substantially expand understanding of the atomic and electronic structure of PtS2 and indicate that STM is a powerful tool capable of locally probing non-uniform polycrystalline films, such as those produced by TAC. Prior to STM/STS measurements the quality of synthesised TAC PtS2 was analysed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. These results are of relevance to applications-focussed studies centred on PtS2 and may inform future efforts to optimise the synthesis conditions for thin film PtS2.

Insights into Multilevel Resistive Switching in Monolayer MoS2.

The advent of two-dimensional materials has opened a plethora of opportunities in accessing ultrascaled device dimensions for future logic and memory applications. In this work, we demonstrate that a single layer of large-area chemical vapor deposition-grown molybdenum disulfide (MoS2) sandwiched between two metal electrodes can be tuned to show multilevel nonvolatile resistive memory states with resistance values separated by 5 orders of magnitude. The switching process is unipolar and thermochemically driven requiring significant Joule heating in the reset process. Temperature-dependent electrical measurements coupled with semiclassical charge transport models suggest that the transport in these devices varies significantly in the initial (pristine) state, high resistance state, and low resistance state. In the initial state, the transport is a one-step direct tunneling (at low voltage biases) and Fowler Nordeim tunneling (at higher bias) with an effective barrier height of 0.33 eV, which closely matches the Schottky barrier at the MoS2/Au interface. In the high resistive state, trap-assisted tunneling provides a reasonable fit to experimental data for a trap height of 0.82 eV. Density functional theory calculations suggest the possibility of single- and double-sulfur vacancies as the microscopic origins of these trap sites. The temperature-dependent behavior of the set and reset process are explained by invoking the probability of defect (sulfur vacancy) creation and mobility of sulfur ions. Finally, conductive atomic force microscopy measurements confirm that the multifilamentary resistive memory effects are inherent to a single-crystalline MoS2 triangle and not necessarily dependent on grain boundaries. The insights suggested in this work are envisioned to open up possibilities for ultrascaled, multistate, resistive memories for next-generation digital memory and neuromorphic applications.

Photoelectrical properties of graphene/doped GeSn vertical heterostructures.

GeSn is a group IV alloy material with a narrow bandgap, making it favorable for applications in sensing and imaging. However, strong surface carrier recombination is a limiting factor. To overcome this, we investigate the broadband photoelectrical properties of graphene integrated with doped GeSn, from the visible to the near infrared. It is found that photo-generated carriers can be separated and transported with a higher efficiency by the introduction of the graphene layer. Considering two contrasting arrangements of graphene on p-type and n-type GeSn films, photocurrents were suppressed in graphene/p-type GeSn heterostructures but enhanced in graphene/n-type GeSn heterostructures when compared with control samples without graphene. Moreover, the enhancement (suppression) factor increases with excitation wavelength but decreases with laser power. An enhancement factor of 4 is achieved for an excitation wavelength of 1064 nm. Compared with previous studies, it is found that our graphene/n-type GeSn based photodetectors provide a much wider photodetection range, from 532 nm to 1832 nm, and maintain comparable responsivity. Our experimental findings highlight the importance of the induced bending profile on the charge separation and provides a way to design high performance broadband photodetectors.

Charge density waves and degenerate modes in exfoliated monolayer 2H-TaS2.

Charge density waves spontaneously breaking lattice symmetry through periodic lattice distortion, and electron-electron and electron-phonon inter-actions, can lead to a new type of electronic band structure. Bulk 2H-TaS2 is an archetypal transition metal dichalcogenide supporting charge density waves with a phase transition at 75 K. Here, it is shown that charge density waves can exist in exfoliated monolayer 2H-TaS2 and the transition temperature can reach 140 K, which is much higher than that in the bulk. The degenerate breathing and wiggle modes of 2H-TaS2 originating from the periodic lattice distortion are probed by optical methods. The results open an avenue to investigating charge density wave phases in two-dimensional transition metal dichalcogenides and will be helpful for understanding and designing devices based on charge density waves.

Enhanced NO2 Sensitivity in Schottky-Contacted n-Type SnS2 Gas Sensors.

Layered materials are highly attractive in gas sensor research due to their extraordinary electronic and physicochemical properties. The development of cheaper and faster room-temperature detectors with high sensitivities especially in the parts per billion level is the main challenge in this rapidly developing field. Here, we show that sensitivity to NO2 (S) can be greatly improved by at least two orders of magnitude using an n-type electrode metal. Unconventionally for such devices, the ln(S) follows the classic Langmuir isotherm model rather than S as is for a p-type electrode metal. Excellent device sensitivities, as high as 13,000% for 9 ppm and 97% for 1 ppb NO2, are achieved with Mn electrodes at room temperature, which can be further tuned and enhanced with the application of a bias. Long-term stability, fast recovery, and strong selectivity toward NO2 are also demonstrated. Such impressive features provide a real solution for designing a practical high-performance layered material-based gas sensor.

Sub-millimeter size high mobility single crystal MoSe2 monolayers synthesized by NaCl-assisted chemical vapor deposition.

Monolayer MoSe2 is a transition metal dichalcogenide with a narrow bandgap, high optical absorbance and large spin-splitting energy, giving it great promise for applications in the field of optoelectronics. Producing monolayer MoSe2 films in a reliable and scalable manner is still a challenging task as conventional chemical vapor deposition (CVD) or exfoliation based techniques are limited due to the small domains/nanosheet sizes obtained. Here, based on NaCl assisted CVD, we demonstrate the simple and stable synthesis of sub-millimeter size single-crystal MoSe2 monolayers with mobilities ranging from 38 to 8 cm2 V-1 s-1. The average mobility is 12 cm2 V-1 s-1. We further determine that the optical responsivity of monolayer MoSe2 is 42 mA W-1, with an external quantum efficiency of 8.22%.

Electrical Contact Barriers between a Three-Dimensional Metal and Layered SnS2.

Field-effect transistors derived from traditional 3D semiconductors are rapidly approaching their fundamental limits. Layered semiconducting materials have emerged as promising candidates to replace restrictive 3D semiconductor materials. However, contacts between metals and layered materials deviate from Schottky-Mott behavior when determined by transport methods, while X-ray photoelectron spectroscopy measurements suggest that the contacts should be at the Schottky limit. Here, we present a systematic investigation on the influence of metal selection when electrically contacting SnS2, a layered metal dichalcogenide semiconductor with the potential to replace silicon. It is found that the electrically measured barrier height depends also weakly on the work function of the metal contacts with slopes of 0.09 and -0.34 for n-type and p-type Schottky contacts, respectively. Based on the Kirchhoff voltage law and considering a current path induced by metallic defects, we found that the Schottky barrier still follows the Schottky-Mott limits and the electrically measured barrier height mainly originates from the van der Waals gap between the metal and SnS2, and the slope depends on the magnitude of the van der Waals capacitance.

Effects of Annealing Temperature and Ambient on Metal/PtSe2 Contact Alloy Formation.

Forming gas annealing is a common process step used to improve the performance of devices based on transition-metal dichalcogenides (TMDs). Here, the impact of forming gas anneal is investigated for PtSe2-based devices. A range of annealing temperatures (150, 250, and 350 °C) were used both in inert (0/100% H2/N2) and forming gas (5/95% H2/N2) environments to separate the contribution of temperature and ambient. The samples are electrically characterized by circular transfer length method structures, from which contact resistance and sheet resistance are analyzed. Ti and Ni are used as metal contacts. Ti does not react with PtSe2 at any given annealing step. In contrast to this, Ni reacts with PtSe2, resulting in a contact alloy formation. The results are supported by a combination of X-ray photoelectron spectroscopy, Raman spectroscopy, energy-dispersive X-ray spectroscopy, and cross-sectional transmission electron microscopy. The work sheds light on the impact of forming gas annealing on TMD-metal interfaces, and on the TMD film itself, which could be of great interest to improve the contact resistance of TMD-based devices.

Enhanced NO2 Sensing at Room Temperature with Graphene via Monodisperse Polystyrene Bead Decoration.

Graphene is a single layer of carbon atoms with a large surface-to-volume ratio, providing a large capacity gas molecule adsorption and a strong surface sensitivity. Chemical vapor deposition-grown graphene-based NO2 gas sensors typically have detection limits from 100 parts per billion (ppb) to a few parts per million (ppm), with response times over 1000 s. Numerous methods have been proposed to enhance the NO2 sensing ability of graphenes. Among them, surface decoration with metal particles and metal-oxide particles has demonstrated the potential to enhance the gas-sensing properties. Here, we show that the NO2 sensing of graphene can be also enhanced via decoration with monodisperse polymer beads. In dark conditions, the detection limit is improved from 1000 to 45 ppb after the application of polystyrene (PS) beads. With laser illumination, a detection limit of 0.5 ppb is determined. The enhanced gas sensing is due to surface plasmon polaritons excited by interference and charge transfer between the PS beads. This method opens an interesting route for the application of graphene in gas sensing.

High Selectivity Gas Sensing and Charge Transfer of SnSe2.

SnSe2 is an anisotropic binary-layered material with rich physics, which could see it used for a variety of potential applications. Here, we investigate the gas-sensing properties of SnSe2 using first-principles calculations and verify predictions using a gas sensor made of few-layer SnSe2 grown by chemical vapor deposition. Theoretical simulations indicate that electrons transfer from SnSe2 to NO2, whereas the direction of charge transfer is the opposite for NH3. Notably, a flat molecular band appears around the Fermi energy after NO2 adsorption and the induced molecular band is close to the conduction band minimum. Moreover, compared with NH3, NO2 molecules adsorbed on SnSe2 have a lower adsorption energy and a higher charge transfer value. The dynamic-sensing responses of SnSe2 sensors confirm the theoretical predictions. The good match between the theoretical prediction and experimental demonstration suggests that the underlying sensing mechanism is related to the charge transfer and induced flat band. Our results provide a guideline for designing high-performance gas sensors based on SnSe2.