High-performance multilayer WSe2/SnS2p-n heterojunction photodetectors by two step confined space chemical vapor deposition.

Two-dimensional (2D) p-n heterojunctions have attracted great attention due to their outstanding properties in electronic and optoelectronic devices, especially in photodetectors. Various types of heterojunctions have been constituted by mechanical exfoliation and stacking. However, achieving controlled growth of heterojunction structures remains a tremendous challenge. Here, we employed a two-step KI-assisted confined-space chemical vapor deposition method to prepare multilayer WSe2/SnS2p-n heterojunctions. Optical characterization results revealed that the prepared WSe2/SnS2vertical heterostructures have clear interfaces as well as vertical heterostructures. The electrical and optoelectronic properties were investigated by constructing the corresponding heterojunction devices, which exhibited good rectification characteristics and obtained a high detectivity of 7.85 × 1012Jones and a photoresponse of 227.3 A W-1under visible light irradiation, as well as a fast rise/fall time of 166/440µs. These remarkable performances are likely attributed to the ultra-low dark current generated in the depletion region at the junction and the high direct tunneling current during illumination. This work demonstrates the value of multilayer WSe2/SnS2heterojunctions for applications in high-performance photodetectors.

High-Responsivity and Broadband MoS2 Photodetector Using Interfacial Engineering.

Combining MoS2 with mature silicon technology is an effective method for preparing high-performance photodetectors. However, the previously studied MoS2/silicon-based heterojunction photodetectors cannot simultaneously demonstrate high responsivity, a fast response time, and broad spectral detection. We constructed a broad spectral n-type MoS2/p-type silicon-based heterojunction photodetector. The SiO2 dielectric layer on the silicon substrate was pretreated with soft plasma to change its thickness and surface state. The pretreated SiO2 dielectric layer and the silicon substrate constitute a multilayer heterostructure with a high carrier concentration and responsiveness. Taking silicon-based and n-type MoS2 heterojunction photodetectors as examples, its responsivity can reach 4.05 × 104 A W1- at 637 nm wavelength with a power density of 2 µW mm-2, and the detectable spectral range is measured from 447 to 1600 nm. This pretreated substrate was proven applicable to other n-type TMDCs, such as MoTe2, ReS2, etc., with certain versatility.

Lithography-free and high-efficiency preparation of black phosphorous devices by direct evaporation through shadow mask.

Two-dimensional (2D) materials including black phosphorus (BP) have been extensively investigated because of their exotic physical properties and potential applications in nanoelectronics and optoelectronics. Fabricating BP based devices is challenging because BP is extremely sensitive to the external environment, especially to the chemical contamination during the lithography process. The direct evaporation through shadow mask technique is a clean method for lithography-free electrode patterning of 2D materials. Herein, we employ the lithography-free evaporation method for the construction of BP based field-effect transistors and photodetectors and systematically compare their performances with those of BP counterparts fabricated by conventional lithography and transfer electrode methods. The results show that BP devices fabricated by direct evaporation method possess higher mobility, faster response time, and smaller hysteresis than those prepared by the latter two methods. This can be attributed to the clean interface between BP and evaporated-electrodes as well as the lower Schottky barrier height of 20.2 meV, which is given by the temperature-dependent electrical results. Furthermore, the BP photodetectors exhibit a broad-spectrum response and polarization sensitivity. Our work elucidates a universal, low-cost and high-efficiency method to fabricate BP devices for optoelectronic applications.

Synthesis and Characterization of Metallic Janus MoSH Monolayer.

Janus transition-metal dichalcogenides (TMDCs) are emerging as special 2D materials with different chalcogen atoms covalently bonded on each side of the unit cell, resulting in interesting properties. To date, several synthetic strategies have been developed to realize Janus TMDCs, which first involves stripping the top-layer S of MoS2 with H atoms. However, there has been little discussion on the intermediate Janus MoSH. It is critical to find the appropriate plasma treatment time to avoid sample damage. A thorough understanding of the formation and properties of MoSH is highly desirable. In this work, a controlled H2-plasma treatment has been developed to gradually synthesize a Janus MoSH monolayer, which was confirmed by the TOF-SIMS analysis as well as the subsequent fabrication of MoSSe. The electronic properties of MoSH, including the high intrinsic carrier concentration (∼2 × 1013 cm-2) and the Fermi level (∼ - 4.11 eV), have been systematically investigated by the combination of FET device study, KPFM, and DFT calculations. The results demonstrate a method for the creation of Janus MoSH and present the essential electronic parameters which have great significance for device applications. Furthermore, owing to the metallicity, 2D Janus MoSH might be a potential platform to observe the SPR behavior in the mid-infrared region.

Status and prospects of Ohmic contacts on two-dimensional semiconductors.

In recent years, two-dimensional materials have received more and more attention in the development of semiconductor devices, and their practical applications in optoelectronic devices have also developed rapidly. However, there are still some factors that limit the performance of two-dimensional semiconductor material devices, and one of the most important is Ohmic contact. Here, we elaborate on a variety of approaches to achieve Ohmic contacts on two-dimensional materials and reveal their physical mechanisms. For the work function mismatch problem, we summarize the comparison of barrier heights between different metals and 2D semiconductors. We also examine different methods to solve the problem of Fermi level pinning. For the novel 2D metal-semiconductor contact methods, we analyse their effects on reducing contact resistance from two different perspectives: homojunction and heterojunction. Finally, the challenges of 2D semiconductors in achieving Ohmic contacts are outlined.

Bidirectional doping of two-dimensional thin-layer transition metal dichalcogenides using soft ammonia plasma.

Because of suitable band gap and high mobility, two-dimensional transition metal dichalcogenide (TMD) materials are promising in future microelectronic devices. However, controllable p-type and n-type doping of TMDs is still a challenge. Herein, we develop a soft plasma doping concept and demonstrate both n-type and p-type doping for TMDs including MoS2 and WS2 through adjusting the plasma working parameters. In particular, p-type doping of MoS2 can be realized when the radio frequency (RF) power is relatively small and the processing time is short: the off-state current increases from ∼10-10 A to ∼10-8 A, the threshold voltage is positively shifted from -26.2 V to 8.3 V, and the mobility increases from 7.05 cm2 V-1 s-1 to 16.52 cm2 V-1 s-1. Under a relatively large RF power and long processing time, n-type doping was realized for MoS2: the threshold voltage was negatively shifted from 6.8 V to -13.3 V and the mobility is reduced from 10.32 cm2 V-1 s-1 to 3.2 cm2 V-1 s-1. For the former, suitable plasma treatment can promote the substitution of N elements for S vacancies and lead to p-type doping, thus reducing the defect density and increasing the mobility value. For the latter, due to excessive plasma treatment, more S vacancies will be produced, leading to heavier n-type doping as well as a decrease in mobility. We confirm the results by systematically analyzing the optical, compositional, thickness and structural characteristics of the samples before and after such soft plasma treatments via Raman, photoluminescence (PL), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) measurements. Due to its nondestructive and expandable nature and compatibility with the current microelectronics industry, this potentially generic method may be used as a reliable technology for the development of diverse and functional TMD-based devices.

Large-scale MoS2(1-x)Se2xmonolayers synthesized by confined-space CVD.

Alloy engineering is efficient in modulating the electronic structure and physical and chemical properties of Transition metal dichalcogenides (TMDs). Here, we develop an efficient and simple confined-space CVD strategy by using a smaller quartz boat nested in a larger quartz boat for the preparation of ternary alloy MoS2(1-x)Se2xmonolayers on SiO2/Si substrates with controllable composition. The effect of hydrogen ratio of the mixed carrier gas (Ar/H2) on the resultant flakes are systematically investigated. A hydrogon ratio of 15% is demonstrated to be the most appropriate to synthesize large size (more than 400µm) single crystalline MoS2(1-x)Se2xalloy monolayers. The composition of the alloy can also be changed in a full range (2x= 0-2) by changing the weight ratio of Se and S powder. The as-grown monolayer MoS2(1-x)Se2xalloys present continuously high crystal quality in terms of Raman and PL measurements. Furthermore, to visible light (532 nm), the MoS2(1-x)Se2xbased photodetectors display wonderful photoresponse with a fast response of less than 50 ms. Our work may be usedful in directing the synthesis of TMDs alloys as well as their optoelectronic applications.

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.

Controllable Epitaxial Growth of Large-Area MoS2 /WS2 Vertical Heterostructures by Confined-Space Chemical Vapor Deposition.

The controllable large-area growth of single-crystal vertical heterostructures based on 2D transition metal dichalcogenides (TMDs) remains a challenge. Here, large-area vertical MoS2 /WS2 heterostructures are synthesized using single-step confined-space chemical vapor epitaxy. The heterostructures can evolve into two different kinds by switching the H2 flow on and off: MoS2 /WS2 heterostructures with multiple WS2 domains can be achieved without introducing the H2 flow due to the numerous nucleation centers on the bottom MoS2 monolayer during the transition stage between the MoS2 and WS2 monolayer growth. In contrast, isolated MoS2 /WS2 heterostructures with single WS2 domain can be obtained with introducing the H2 flow due to the reduced nucleation centers on the bottom MoS2 monolayer arising from the hydrogen etching effect. Both the two kinds of the vertical MoS2 /WS2 heterostructures feature high quality. The photodetectors based on the isolated MoS2 /WS2 heterostructures exhibit a high responsivity of 68 mA W-1 and a short response time of 35 ms. This single-step chemical vapor epitaxy can be used to synthesize vertical MoS2 /WS2 heterostructures with high production efficiency. The new epitaxial growth approach may open new pathways to fabricate large-area heterostructures made of different 2D TMDs monolayers of interest to electronics, optoelectronics, and other applications.

High performance IGZO-based phototransistors by BN/BP interface engineering.

Some advances have been achieved in developing heterojunctions consisting of indium-gallium-zinc oxide (a-IGZO) films and two dimensional (2D) van der Waals materials for optoelectronic applications in recent years, however, the improvement of IGZO channel itself via constructing such heterojunctions is rarely reported. Here, we report the huge improvement in photoresponse performances for the IGZO phototransistor devices by introducing boron nitride (BN)/black phosphorus (BP) interface engineering. By creating an appropriate band bending and an efficient photo-generated carrier transfer path between IGZO and BP, the recombination of the photo-generated carriers in the IGZO channel is significantly suppressed. As a result, the corresponding photoresponsivity at a wavelength of 447 nm can be promoted from 0.05 A W-1 to 0.3 A W-1. A corresponding maximum external quantum efficiency of 83.4% was obtained for the BN/BP decorated IGZO phototransistor. The results imply that such interface engineering via 2D materials can be used as a general route to high performance oxide-semiconductor based optoelectronic devices.

2D atomic crystal molecular superlattices by soft plasma intercalation.

Two-dimensional (2D) atomic crystal superlattices integrate diverse 2D layered materials enabling adjustable electronic and optical properties. However, tunability of the interlayer gap and interactions remain challenging. Here we report a solution based on soft oxygen plasma intercalation. 2D atomic crystal molecular superlattices (ACMSs) are produced by intercalating O2+ ions into the interlayer space using the plasma electric field. Stable molecular oxygen layer is formed by van der Waals interactions with adjacent transition metal dichalcogenide (TMD) monolayers. The resulting interlayer gap expansion can effectively isolate TMD monolayers and impart exotic properties to homo-(MoS2[O2]x) and hetero-(MoS2[O2]x/WS2[O2]x) stacked ACMSs beyond typical capacities of monolayer TMDs, such as 100 times stronger photoluminescence and 100 times higher photocurrent. Our potentially universal approach to tune interlayer stacking and interactions in 2D ACMSs may lead to exotic superlattice properties intrinsic to monolayer materials such as direct bandgap pursued for future optoelectronics.

InvivoPen: A novel plasma source for in vivo cancer treatment.

Background: With the anti-cancer efficacies of cold atmospheric plasma being increasingly recognized in vitro, a demand on creating an effective tool feasible for in vivo animal treatment has emerged. Methods: Through the use of co-axial needles with different calibers in diameter, we designed a novel in situ ejection source of cold atmospheric plasma, namely invivoPen, for animal experiments. It punches just a single pinhole that could considerably ease the complexity of operating with small animals such as mouse. Results: We showed that invivoPen could deliver similar efficacies as plasma activated medium with reduced cost in suppressing cell proliferation and migration as well as potentially boosting the viabilities of mice receiving invivoPen treatment. Blood test, renal and liver functionalities tests all suggest that physical plasma could effectively return tumor-carrying mice to the healthy state without harm to body conditions, and invivoPen slightly outweighs PAM in boosting animal immunity and reducing inflammation. Conclusion: Our study contributes to the community in providing a minimal invasive in situ plasma source, having partly explained the efficacies of cold atmospheric plasma in treating triple negative breast cancers, and proposing the potential synergies between physical plasma and conventional drugs for cancer treatment.

Two-Dimensional Alloying Molybdenum Tin Disulfide Monolayers with Fast Photoresponse.

Elemental alloying in monolayer, two-dimensional (2D) transition metal dichalcogenides (TMDs) promises unprecedented ability to modulate their electronic structure leading to unique optoelectronic properties. MoS2 monolayer based photodetectors typically exhibit a high photoresponsivity but suffer from a low response time. Here we develop a new approach for Sn alloying in MoS2 monolayers based on the synergy of the customized chemical vapor deposition (CVD) and the effects of common salt (NaCl) to produce high-quality and large-size Mo1-xSnxS2 (x < 0.5) alloy monolayers. The composition difference results in different growth behaviors; Mo dominated alloys (x < 0.5) exhibit uniform and large size (up to 100 µm) triangular monolayers, while Sn-dominated alloys (x > 0.5) present multilayer grains. The Mo1-xSnxS2 (x < 0.5) based photodetectors and phototransistors exhibit a maximum responsitivity of 12 mA/W and a minimum response time of 20 ms, which is faster than most reported MoS2-based photodetectors. This work offers new perspectives for precision 2D alloy engineering to improve the optoelectronic performance of TMD-based photodetectors.

Prussian blue analogue nanoenzymes mitigate oxidative stress and boost bio-fermentation.

Oxidative stress in cells caused by the accumulation of reactive oxygen species (ROS) is a common cause of cell function degeneration, cell death and various diseases. Efficient, robust and inexpensive nanoparticles (nanoenzymes) capable of scavenging/detoxifying ROS even in harsh environments are attracting strong interest. Prussian blue analogues (PBAs), a prominent group of metalorganic nanoparticles (NPs) with the same cyanometalate structure as the traditional and commonly used Prussian blue (PB), have long been envisaged to mimic enzyme activities for ROS scavenging. However, their biological toxicity, especially potential effects on living beings during practical application, has not yet been fully investigated. Here we reveal the enzyme-like activity of FeCo-PBA NPs, and for the first time investigate the effects of FeCo-PBA on cell viability and growth. We elucidate the effect of the nanoenzyme on the ethanol-production efficacy of a typical model organism, the engineered industrial strain Saccharomyces cerevisiae. We further demonstrate that FeCo-PBA NPs have almost no cytotoxicity on the cells over a broad dosage range (0-100 µg mL-1), while clearly boosting the yeast fermentation efficiency by mitigating oxidative stress. Atmospheric pressure cold plasma (APCP) pretreatment is used as a multifunctional environmental stress produced by the plasma reactive species. While the plasma enhances the cellular uptake of NPs, FeCo-PBA NPs protect the cells from the oxidative stress induced by both the plasma and the fermentation processes. This synergistic effect leads to higher secondary metabolite yields and energy production. Collectively, this study confirms the positive effects of PBA nanoparticles in living cells through ROS scavenging, thus potentially opening new ways to control the cellular machinery in future nano-biotechnology and nano-biomedical applications.

Recent advances in plasma modification of 2D transition metal dichalcogenides.

Two-dimensional (2D) transition metal dichalcogenide (TMDC) materials have recently attracted great interest because of their tantalising prospects for a broad range of applications including electronics, optoelectronics, and energy storage. Unlike bulk materials, the device performance of atomically thin 2D materials is determined by the interface, thickness and defects. Plasma processing is very effective for diverse modifications of nanoscale 2D TMDC materials, owing to its uniquely controllable, effective processes and energy efficiency. Herein, we critically discuss selected recent advances in plasma modification of 2D TMDC materials and their optical and electronic (including optoelectronic) properties of relevance to applications in hydrogen production, gas sensing and energy storage devices. Challenges and future research opportunities in the relevant research field are presented. This review contributes to directing future advances of plasma processing of TMDC materials for targeted applications.

Transition metal dichalcogenides bilayer single crystals by reverse-flow chemical vapor epitaxy.

Epitaxial growth of atomically thin two-dimensional crystals such as transition metal dichalcogenides remains challenging, especially for producing large-size transition metal dichalcogenides bilayer crystals featuring high density of states, carrier mobility and stability at room temperature. Here we achieve in epitaxial growth of the second monolayer from the first monolayer by reverse-flow chemical vapor epitaxy and produce high-quality, large-size transition metal dichalcogenides bilayer crystals with high yield, control, and reliability. Customized temperature profiles and reverse gas flow help activate the first layer without introducing new nucleation centers leading to near-defect-free epitaxial growth of the second layer from the existing nucleation centers. A series of bilayer crystals including MoS2 and WS2, ternary Mo1-xWxS2 and quaternary Mo1-xWxS2(1-y)Se2y are synthesized with variable structural configurations and tunable electronic and optical properties. The robust, potentially universal approach for the synthesis of large-size transition metal dichalcogenides bilayer single crystals is highly-promising for fundamental studies and technological applications.

Soft hydrogen plasma induced phase transition in monolayer and few-layer MoTe2.

Phase transition from the semiconducting hexagonal (2H) phase to the metallic monoclinic (1T') phase in two-dimensional (2D) transition metal dichalcogenides like MoTe2 is not only of great importance in fundamental study but also of technological significance for broad device applications. Here we report a universal, facile, scalable and reversible phase engineering technique (between 2H and 1T' phases) for both monolayer and few-layer MoTe2 based on a soft hydrogen plasma treatment. The 2H â†’ 1T' transition was confirmed by a series of characterizations including Raman spectra and mapping studies, XPS analysis and FET device measurements at varying temperatures. We attribute the phase transition to the warping of Te-Mo bonds and the lateral sliding of the top Te-layer induced by the soft hydrogen ion bombardment according to both the structural and electronic characterizations as well as the horizontal comparison with the cases of Ar or O2 plasma treatment. We have also prepared a 2D heterostructure containing periodical 2H and 1T' MoTe2 and showed that such phase transition can be readily reversed by post annealing. These results thus provide a robust and efficient approach for the phase engineering of monolayer and few-layer MoTe2 and could aid the development of 2D optoelectronic, memory and reconfigurable devices.

The effect of graphene on surface plasmon resonance of metal nanoparticles.

Two transparent graphene-metal nanoparticle (NP) hybrid schemes, namely Au NPs covered by graphene layers and Au NPs encapsulated by graphene layers, are presented and the effect of graphene on the localized surface plasmon resonance of metal NPs is systematically investigated. For both schemes, the direct contact of graphene with Au NPs would strongly tune the resonant frequency due to the electron transfer from Au NPs to graphene. Such electron transfer is demonstrated by comparing the absorption spectra of Au NPs with different free electron densities between calculation results via FDTD simulation and experimental results, comparing Raman properties of graphene between pure graphene and the Au-NP/graphene hybrid nanostructure, correlating the electron doping concentration in graphene with the electron density change in Au NPs, and ruling out the possible mechanism of the change of the effective refractive index of Au NPs. Such an effective tuning of the resonant frequency may shed light on the future applications of 2D based materials in plasmonic devices.

Controllable one-step growth of bilayer MoS2-WS2/WS2 heterostructures by chemical vapor deposition.

Heterostructures of two-dimensional (2D) transition metal dichalcogenides (TMDs) offer attractive prospects for practical applications by combining unique physical properties that are distinct from those of traditional structures. In this paper, we demonstrate a three-stage chemical vapor deposition method for the growth of bilayer MoS2-WS2/WS2 heterostructures with the bottom layers being the lateral MoS2-center/WS2-edge monolayer heterostructures and the top layers being the WS2 monolayers. The alternative growth of lateral and vertical heterostructures can be realized by adjusting both the temperature and the carrier gas flow direction. The combined effect of both reverse gas flow and higher growing temperature can promote the epitaxial growth of second layer on the activated nucleation centers of the first monolayer heterostructures. By using customized temperature profiles, single heterostructures including monolayer lateral MoS2-WS2 heterostructures and bilayer lateral WS2(2L)-MoS2(2L) heterostructures could also be obtained. Atomic force microscopy, photoluminescence and Raman mapping studies clearly reveal that these different heterostructure samples are highly uniform. These results thus provide a promising and efficient method for the synthesis of complex heterostructures based on different TMDs materials, which would greatly expand the heterostructure family and broaden their applications.

Shape-Uniform, High-Quality Monolayered MoS2 Crystals for Gate-Tunable Photoluminescence.

Two-dimensional molybdenum disulfide (MoS2) has recently drawn major attention due to its promising applications in electronics and optoelectronics. Chemical vapor deposition (CVD) is a scalable method to produce large-area MoS2 monolayers, yet it is challenging to achieve shape-uniform, high-quality monolayered MoS2 grains as random, diverse crystallographic orientations and various shapes are produced in the same CVD process. Here, we report the growth of high-quality MoS2 monolayers with uniform triangular shapes dominating (up to 89%) over other shapes on both SiO2/Si and sapphire substrates. The new confined-space CVD process prevents contamination and helps regulate the Mo/S ratio during the deposition. The as-grown triangular MoS2 monolayers exhibit grain sizes up to 150 µm and possess better crystalline properties and lighter n-type doping concentration than those of the monolayers grown by common CVD methods. The corresponding field effect transistor devices show high electron mobilities of 50-60 cm2 V-1 s-1 and positive threshold voltages of 21-35 V. This mild n-type behavior makes it possible to regulate the formation of excitons by back-gate voltage due to the interaction of excitons with free charge carriers in the MoS2 channel. As a result, gate-tunable photoluminescence (PL) effect, which is rarely achievable for MoS2 samples prepared by common CVD or mechanical exfoliation, is demonstrated. This study provides a simple versatile approach to fabricating monolayered crystals of MoS2 and other high-quality transition metal dichalcogenides and could lead to new optoelectronic devices based on gate-tunable PL effect.