Photoswitchable optoelectronic properties of 2D MoSe2/diarylethene hybrid structures.

The ability to modulate optical and electrical properties of two-dimensional (2D) semiconductors has sparked considerable interest in transition metal dichalcogenides (TMDs). Herein, we introduce a facile strategy for modulating optoelectronic properties of monolayer MoSe2 with external light. Photochromic diarylethene (DAE) molecules formed a 2-nm-thick uniform layer on MoSe2, switching between its closed- and open-form isomers under UV and visible irradiation, respectively. We have discovered that the closed DAE conformation under UV has its lowest unoccupied molecular orbital energy level lower than the conduction band minimum of MoSe2, which facilitates photoinduced charge separation at the hybrid interface and quenches photoluminescence (PL) from monolayer flakes. In contrast, open isomers under visible light prevent photoexcited electron transfer from MoSe2 to DAE, thus retaining PL emission properties. Alternating UV and visible light repeatedly show a dynamic modulation of optoelectronic signatures of MoSe2. Conductive atomic force microscopy and Kelvin probe force microscopy also reveal an increase in conductivity and work function of MoSe2/DAE with photoswitched closed-form DAE. These results may open new opportunities for designing new phototransistors and other 2D optoelectronic devices.

Advances in Two-Dimensional Magnetic Semiconductors via Substitutional Doping of Transition Metal Dichalcogenides.

Transition metal dichalcogenides (TMDs) are two-dimensional (2D) materials with remarkable electrical, optical, and chemical properties. One promising strategy to tailor the properties of TMDs is to create alloys through a dopant-induced modification. Dopants can introduce additional states within the bandgap of TMDs, leading to changes in their optical, electronic, and magnetic properties. This paper overviews chemical vapor deposition (CVD) methods to introduce dopants into TMD monolayers, and discusses the advantages, limitations, and their impacts on the structural, electrical, optical, and magnetic properties of substitutionally doped TMDs. The dopants in TMDs modify the density and type of carriers in the material, thereby influencing the optical properties of the materials. The magnetic moment and circular dichroism in magnetic TMDs are also strongly affected by doping, which enhances the magnetic signal in the material. Finally, we highlight the different doping-induced magnetic properties of TMDs, including superexchange-induced ferromagnetism and valley Zeeman shift. Overall, this review paper provides a comprehensive summary of magnetic TMDs synthesized via CVD, which can guide future research on doped TMDs for various applications, such as spintronics, optoelectronics, and magnetic memory devices.

An Ultralow Power Mixed Dimensional Heterojunction Transistor Based on the Charge Plasma pn Junction.

Development of a reliable doping method for 2D materials is a key issue to adopt the materials in the future microelectronic circuits and to replace the silicon, keeping the Moore's law toward the sub-10 nm channel length. Especially hole doping is highly required, because most of the transition metal dichalcogenides (TMDC) among the 2D materials are electron-doped by sulfur vacancies in their atomic structures. Here, hole doping of a TMDC, tungsten disulfide (WS2 ) using the silicon substrate as the dopant medium is demonstrated. An ultralow-power current sourcing transistor or a gated WS2 pn diode is fabricated based on a charge plasma pn heterojunction formed between the WS2 thin-film and heavily doped bulk silicon. An ultralow switchable output current down to 0.01 nA µm-1 , an off-state current of ≈1 × 10-14 A µm-1 , a static power consumption range of 1 fW µm-1 -1 pW µm-1 , and an output current ratio of 103 at 0.1 V supply voltage are achieved. The charge plasma heterojunction allows a stable (less than 3% variation) output current regardless of the gate voltage once it is turned on.

Radiative pattern of intralayer and interlayer excitons in two-dimensional WS2/WSe2 heterostructure.

Two-dimensional (2D) heterostructures (HS) formed by transition-metal dichalcogenide (TMDC) monolayers offer a unique platform for the study of intralayer and interlayer excitons as well as moiré-pattern-induced features. Particularly, the dipolar charge-transfer exciton comprising an electron and a hole, which are confined to separate layers of 2D semiconductors and Coulomb-bound across the heterojunction interface, has drawn considerable attention in the research community. On the one hand, it bears significance for optoelectronic devices, e.g. in terms of charge carrier extraction from photovoltaic devices. On the other hand, its spatially indirect nature and correspondingly high longevity among excitons as well as its out-of-plane dipole orientation render it attractive for excitonic Bose-Einstein condensation studies, which address collective coherence effects, and for photonic integration schemes with TMDCs. Here, we demonstrate the interlayer excitons' out-of-plane dipole orientation through angle-resolved spectroscopy of the HS photoluminescence at cryogenic temperatures, employing a tungsten-based TMDC HS. Within the measurable light cone, the directly-obtained radiation profile of this species clearly resembles that of an in-plane emitter which deviates from that of the intralayer bright excitons as well as the other excitonic HS features recently attributed to artificial superlattices formed by moiré patterns.

Au-on-Ag nanostructure forin-situSERS monitoring of catalytic reactions.

Dual-functionality Au-on-Ag nanostructures (AOA) were fabricated on a silicon substrate by first immobilizing citrate-reduced Ag nanoparticles (Ag NPs, ∼43 nm in diameter), followed by depositing ∼7 nm Au nanofilms (Au NFs) via thermal evaporation. Au NFs were introduced for their catalytic activity in concave-convex nano-configuration. Ag NPs underneath were used for their significant enhancement factor (EF) in surface-enhanced Raman scattering (SERS)-based measurements of analytes of interest. Rhodamine 6G (R6G) was utilized as the Raman-probe to evaluate the SERS sensitivity of AOA. The SERS EF of AOA is ∼37 times than that of Au NPs. Using reduction of 4-nitrothiophenol (4-NTP) by sodium borohydride (NaBH4) as a model reaction, we demonstrated the robust catalytic activity of AOA as well as its capacity to continuously monitor via SERS the disappearance of reactant 4-NTP, emergence and disappearance of intermediate 4,4'-DMAB, and the appearance of product 4-ATP throughout the reduction process in real-time andin situ.

Improving the Optical Quality of MoSe2 and WS2 Monolayers with Complete h-BN Encapsulation by High-Temperature Annealing.

We improved the optical quality and stability of an exfoliated monolayer (ML) MoSe2 and chemical vapor deposition (CVD)-grown WS2 MLs by encapsulating and sealing them with both top and bottom few-layer h-BN, as tested by subsequent high-temperature annealing up to 873 K and photoluminescence (PL) measurements. These transition-metal dichalcogenide (TMD) MLs remained stable up to this maximum temperature, as seen visually. After the heating/cooling cycle, the integrated photoluminescence (PL) intensity at 300 K in the MoSe2 ML was ∼4 times larger than that before heating and that from exciton and trion PL in the analogous WS2 ML sample was ∼14 times and ∼2.5 times larger at 77 K and the exciton peak was ∼9.5 times larger at 300 K. This is attributed to the reduction of impurities, the lateral expulsion of contamination leading to clean and atomically flat surfaces, and the sealing provided by the h-BN layers that prevents the diffusion of molecules such as trace O2 and H2O to the TMD ML. Stability and optical performance are much improved compared to that in earlier work using top h-BN only, in which the WS2 ML PL intensity decreased even for an optimal gas environment. This complete encapsulation is particularly promising for CVD-grown TMD MLs because they have relatively more charge and other impurities than do exfoliated MLs. These results open a new route for improving the optical properties of TMD MLs and their performance and applications both at room and higher temperatures.

Stabilization of Chemical-Vapor-Deposition-Grown WS2 Monolayers at Elevated Temperature with Hexagonal Boron Nitride Encapsulation.

Chemical vapor deposition (CVD)-grown flakes of high-quality monolayers of WS2 can be stabilized at elevated temperatures by encapsulation with several layer hexagonal boron nitride (h-BN), but to different degrees in the presence of ambient air, flowing N2, and flowing forming gas (95% N2, 5% H2). The best passivation of WS2 at elevated temperature occurs for h-BN-covered samples with flowing N2 (after heating to 873 K), as judged by optical microscopy and photoluminescence (PL) intensity after a heating/cooling cycle. Stability is worse for uncovered samples, but best with flowing forming gas. PL from trions, in addition to that from excitons, is seen for covered WS2 only for forming gas, during cooling below ∼323 K; the trion has an estimated binding energy of ∼28 meV. It might occur because of doping level changes caused by charge defect generation by H2 molecules diffusing between the h-BN and the SiO2/Si substrate. The decomposition of uncovered WS2 flakes in air suggests a dissociation and chemisorption energy barrier of O2 on the WS2 surface of ∼1.6 eV. Fitting the high-temperature PL intensities in air gives a binding energy of a free exciton of ∼229 meV.

Experimental and Computational Investigation of Layer-Dependent Thermal Conductivities and Interfacial Thermal Conductance of One- to Three-Layer WSe2.

Two-dimensional materials such as graphene and transition metal dichalcogenides (TMDCs) have received extensive research interest and investigations in the past decade. In this research, we used a refined opto-thermal Raman technique to explore the thermal transport properties of one popular TMDC material WSe2, in the single-layer (1L), bilayer (2L), and trilayer (3L) forms. This measurement technique is direct without additional processing to the material, and the absorption coefficient of WSe2 is discovered during the measurement process to further increase this technique's precision. By comparing the sample's Raman spectroscopy spectra through two different laser spot sizes, we are able to obtain two parameters-lateral thermal conductivities of 1L-3L WSe2 and the interfacial thermal conductance between 1L-3L WSe2 and the substrate. We also implemented full-atom nonequilibrium molecular dynamics simulations (NEMD) to computationally investigate the thermal conductivities of 1L-3L WSe2 to provide comprehensive evidence and confirm the experimental results. The trend of the layer-dependent lateral thermal conductivities and interfacial thermal conductance of 1L-3L WSe2 is discovered. The room-temperature thermal conductivities for 1L-3L WSe2 are 37 ± 12, 24 ± 12, and 20 ± 6 W/(m·K), respectively. The suspended 1L WSe2 possesses a thermal conductivity of 49 ± 14 W/(m·K). Crucially, the interfacial thermal conductance values between 1L-3L WSe2 and the substrate are found to be 2.95 ± 0.46, 3.45 ± 0.50, and 3.46 ± 0.45 MW/(m2·K), respectively, with a flattened trend starting the 2L, a finding that provides the key information for thermal management and thermoelectric designs.

The effects of substitutional Fe-doping on magnetism in MoS2and WS2monolayers.

Doping of two-dimensional (2D) semiconductors has been intensively studied toward modulating their electrical, optical, and magnetic properties. While ferromagnetic 2D semiconductors hold promise for future spintronics and valleytronics, the origin of ferromagnetism in 2D materials remains unclear. Here, we show that substitutional Fe-doping of MoS2and WS2monolayers induce different magnetic properties. The Fe-doped monolayers are directly synthesized via chemical vapor deposition. In both cases, Fe substitutional doping is successfully achieved, as confirmed using scanning transmission electron microscopy. While both Fe:MoS2and Fe:WS2show PL quenching and n-type doping, Fe dopants in WS2monolayers are found to assume deep-level trap states, in contrast to the case of Fe:MoS2, where the states are found to be shallow. Usingµm- and mm-precision local NV-magnetometry and superconducting quantum interference device, we discover that, unlike MoS2monolayers, WS2monolayers do not show a magnetic phase transition to ferromagnetism upon Fe-doping. The absence of ferromagnetism in Fe:WS2is corroborated using density functional theory calculations.

Computational study of the water-driven graphene wrinkle life-cycle towards applications in flexible electronics.

The ubiquitous presence of wrinkles in two-dimensional materials alters their properties significantly. It is observed that during the growth process of graphene, water molecules, sourced from ambient humidity or transferred method used, can get diffused in between graphene and the substrate. The water diffusion causes/assists wrinkle formation in graphene, which influences its properties. The diffused water eventually dries, altering the geometrical parameters and properties of wrinkled graphene nanoribbons. Our study reveals that the initially distributed wrinkles tend to coalesce to form a localized wrinkle whose configuration depends on the initial wrinkle geometry and the quantity of the diffused water. The movement of the localized wrinkle is categorized into three modes-bending, buckling, and sliding. The sliding mode is characterized in terms of velocity as a function of diffused water quantity. Direct bandgap increases linearly with the initial angle except the highest angle considered (21°), which can be attributed to the electron tunneling effect observed in the orbital analysis. The system becomes stable with an increase in the initial angle of wrinkle as observed from the potential energy plots extracted from MD trajectories and confirmed with the DOS plot. The maximum stress generated is less than the plastic limit of the graphene.

Enabling room temperature ferromagnetism in monolayer MoS2 via in situ iron-doping.

Two-dimensional semiconductors, including transition metal dichalcogenides, are of interest in electronics and photonics but remain nonmagnetic in their intrinsic form. Previous efforts to form two-dimensional dilute magnetic semiconductors utilized extrinsic doping techniques or bulk crystal growth, detrimentally affecting uniformity, scalability, or Curie temperature. Here, we demonstrate an in situ substitutional doping of Fe atoms into MoS2 monolayers in the chemical vapor deposition growth. The iron atoms substitute molybdenum sites in MoS2 crystals, as confirmed by transmission electron microscopy and Raman signatures. We uncover an Fe-related spectral transition of Fe:MoS2 monolayers that appears at 2.28 eV above the pristine bandgap and displays pronounced ferromagnetic hysteresis. The microscopic origin is further corroborated by density functional theory calculations of dipole-allowed transitions in Fe:MoS2. Using spatially integrating magnetization measurements and spatially resolving nitrogen-vacancy center magnetometry, we show that Fe:MoS2 monolayers remain magnetized even at ambient conditions, manifesting ferromagnetism at room temperature.

Controlled edge dependent stacking of WS2-WS2 Homo- and WS2-WSe2 Hetero-structures: A Computational Study.

Transition Metal Dichalcogenides (TMDs) are one of the most studied two-dimensional materials in the last 5-10 years due to their extremely interesting layer dependent properties. Despite the presence of vast research work on TMDs, the complex relation between the electro-chemical and physical properties make them the subject of further research. Our main objective is to provide a better insight into the electronic structure of TMDs. This will help us better understand the stability of the bilayer post growth homo/hetero products based on the various edge-termination, and different stacking of the two layers. In this regard, two Tungsten (W) based non-periodic chalcogenide flakes (sulfides and selenides) were considered. An in-depth analysis of their different edge termination and stacking arrangement was performed via Density Functional Theory method using VASP software. Our finding indicates the preference of chalcogenide (c-) terminated structures over the metal (m-) terminated structures for both homo and heterobilayers, and thus strongly suggests the nonexistence of the m-terminated TMDs bilayer products.

Conceptual design considerations for a wireless intraocular pressure sensor system for effective glaucoma management.

As a leading form of preventable visual impairment, it is imperative to assess glaucoma treatment as a function of intraocular pressure (IOP). IOP can spike throughout the day. This necessitates a device that can (1) monitor IOP outside of clinical visits by providing a memory when IOP exceeds a set threshold indicating the possibility for glaucomatous damage to occur; and (2) accurately assess IOP. Both requirements point ultimately towards the development of an implantable device. The Wireless Intraocular Pressure Sensor System (WIPSS) devised by our team uses optical technologies and may assist an overseeing clinician with assessing glaucoma treatment efficacy and avoiding irreversible glaucomatous visual field loss downstream.

A stretchable and bendable all-solid-state pseudocapacitor with dodecylbenzenesulfonate-doped polypyrrole-coated vertically aligned carbon nanotubes partially embedded in PDMS.

We present an all-solid-state flexible and stretchable pseudocapacitor composed of dodecylbenzenesulfonate-doped polypyrrole (PPy(DBS))-coated vertically aligned carbon nanotubes (VACNTs) partially embedded in a polydimethylsiloxane (PDMS) substrate. VACNTs are grown via atmospheric-pressure chemical vapor deposition on a Si/SiO2 substrate and transferred onto PDMS. Then, the PPy(DBS) film is coated with a surface charge of 300 mC cm-2 on individual carbon nanotubes (CNTs) via electropolymerization. The partial embedment of VACNTs in PDMS permits a rapid and facile integration of the PPy(DBS)/CNTs/PDMS structure to construct a flexible and stretchable supercapacitor electrode. The measured capacitance is 3.6 mF cm-2 with a PVA-KOH gel electrolyte at a scan rate of 100 mV s-1, which is maintained under stretching from 0% to 150% and bending/twisting angles from 0° to 180°. This all-solid-state stretchable supercapacitor shows a stable galvanostatic performance during 10 000 charge/discharge cycles with its capacitance retained at 109%.

A carbon nanotube-embedded conjugated polymer mesh with controlled oil absorption and surface regeneration via in situ wettability switch.

This paper presents a mesh-type absorbent made of a carbon nanotube (CNT)-embedded polypyrrole dodecylbenzenesulfonate (PPy(DBS)) surface for controlled absorption and release of oils and regeneration of polymer surfaces toward continuous oil/water separation. The mesh absorbs dichloromethane (DCM) under oxidation in aqueous environment and releases them under reduction via in situ switching of underwater wettability. CNTs were grown out of stainless steel surfaces and embedded into the PPy(DBS) film, which enhanced the switchable wettability as well as the surface regeneration. The CNT-embedded morphology improved oil retention by a factor of two in an oxidized state and decreased wettability switch time by 16% in a reduced state over the mesh without CNT embedment during 250 redox cyclic testing. A rolled 2 cm × 3 cm CNT-embedded PPy(DBS) mesh was furthermore used to demonstrate the continuous absorption and release of oils, during which DCM of 16 times of the absorbent weight was collected in 50 redox cycles.

Influence of Transition Metal Dichalcogenide Surfaces on Cellular Morphology and Adhesion.

This article presents the effect of transition metal dichalcogenide (TMD) surfaces and their geometric arrangements on resulting cellular morphology and adhesion. WS2 and MoS2 on SiO2 and polydimethylsiloxane (PDMS) substrates were utilized as cell culture platforms, and cell-substrate interactions were probed via analysis of cellular morphometric features (i.e., cell area and circularity) of neonatal human dermal fibroblasts (NHDFs) and metrology of TMD surfaces. It was quantitatively confirmed that the presence of TMDs on substrates resulted in an overall enhanced cellular morphology, even on SiO2 substrates adverse to cellular adhesion. On a localized scale, distinct TMD geometric features at sites of adhesion were measured and correlated with the observed cell morphology. Geometric parameters of TMDs, including TMD island count and total TMD area, exhibited positive correlations with the resulting morphology of cells by enhancing cellular areas and elongations. Further, geometric properties were compared to cell area per TMD island, and positive correlations were observed with TMD island size parameters. Cells adhered at heterogeneous locations with combinations of exposed TMD and SiO2, demonstrating an enhanced morphology in relation to the number of TMD islands in a cell's local area and the geometric size parameters of TMD islands within the cell's operating length scale. The proposed mechanisms of cellular adhesion on TMD-modified surfaces are attributed to the role of surface properties (e.g., stiffness, friction, and hydrophobicity) of TMD and underlying SiO2 and their combined effects during progressive stages of cellular adhesion. These findings provide insight toward possibilities of tailoring adhesion of cells guided by geometric parameters of TMDs.

Reduction in Step Height Variation and Correcting Contrast Inversion in Dynamic AFM of WS2 Monolayers.

A model has been developed to account for and prevent the anomalies encountered in topographic images of transition metal dichalcogenide monolayers using dynamic atomic force microscopy (dAFM). The height of WS2 monolayers measured using dAFM appeared to be increased or decreased, resulting from the interactions between the tip and the surface. The hydrophilic SiO2 substrate appeared higher than the weakly hydrophilic WS2 when the tip amplitude was low or at a high set point (high force). Large amplitudes and low set points corrected the step height inversion, but did not recover the true step height. Removing water from the sample resulted in an order of magnitude reduced variation in step height, but the WS2 appeared inverted except at low amplitudes and high set points. Our model explains the varying step heights in dAFM of TMDs as a result of varying tip-sample interactions between the sample and substrate, in the presence or absence of capillaries. To eliminate contrast inversion, high amplitudes can be used to reduce the effect of capillary forces. However, when capillaries are not present, low amplitudes and high set points produce images with proper contrast due to tool operation in the repulsive regime on both materials.

Graphene-vertically aligned carbon nanotube hybrid on PDMS as stretchable electrodes.

Stretchable electrodes are a critical component for flexible electronics such as displays, energy devices, and wearable sensors. Carbon nanotubes (CNTs) and graphene have been considered for flexible electrode applications, due to their mechanical strength, high carrier mobility, and excellent thermal conductivity. Vertically aligned carbon nanotubes (VACNTs) provide the possibility to serve as interconnects to graphene sheets as stretchable electrodes that could maintain high electrical conductivity under large tensile strain. In this work, a graphene oxide (GO)-VACNT hybrid on a PDMS substrate was demonstrated. Here, 50 µm long VACNTs were grown on a Si/SiO2 wafer substrate via atmospheric pressure chemical vapor deposition. VACNTs were directly transferred by delamination from the Si/SiO2 to a semi-cured PDMS substrate, ensuring strong adhesion between VACNTs and PDMS upon full curing of the PDMS. GO ink was then printed on the surface of the VACNT carpet and thermally reduced to reduced graphene oxide (rGO). The sheet resistance of the rGO-VACNT hybrid was measured under uniaxial tensile strains up to 300% applied to the substrate. Under applied strain, the rGO-VACNT hybrid maintained a sheet resistant of 386 ± 55 Ω/sq. Cyclic stretching of the rGO-VACNT hybrid was performed with up to 50 cycles at 100% maximum tensile strain, showing no increase in sheet resistance. These results demonstrate promising performance of the rGO-VACNT hybrid for flexible electronics applications.

Nanotexturing of Conjugated Polymers via One-Step Maskless Oxygen Plasma Etching for Enhanced Tunable Wettability.

A one-step maskless oxygen plasma etching process is investigated to nanopattern conjugated polymer dodecylbenzenesulfonate doped polypyrrole (PPy(DBS)) and to examine the effects of nanostructures on the inherent tunable wettability of the surface and the droplet mobility. Etching characteristics such as the geometry and dimensions of the nanostructures are systematically examined for the etching power and duration. The mechanism of self-formation of vertically aligned dense-array pillared nanostructures in the one-step maskless oxygen plasma etching process is also investigated. Results show that lateral dimensions such as the periodicity and diameter of the pillared nanostructures are insensitive to the etching power and duration, whereas the length and aspect ratio of the nanostructures increase with them. X-ray photoelectron spectroscopy analysis and thermal treatment of the polymer reveal that the codeposition of impurities on the surface resulting from the holding substrate is the primary reason for the self-formation of nanostructures during the oxygen plasma etching, whereas the local crystallinity subject to thermal treatment has a minor effect on the lateral dimensions. Retaining the tunable wettability (oleophobicity) for organic droplets during the electrochemical redox (i.e., reduction and oxidization) process, the nanotextured PPy(DBS) surface shows significant enhancement of droplet mobility compared to that of the flat PPy(DBS) surface with no nanotexture by making the surface superoleophobic (i.e., in a Cassie-Baxter wetting state). Such enhancement of the tunable oleophobicity and droplet mobility of the conjugated polymer will be of great significance in many applications such as microfluidics, lab-on-a-chip devices, and water/oil treatment.

On-Demand Capture and Release of Organic Droplets Using Surfactant-Doped Polypyrrole Surfaces.

In this paper, we demonstrate the controlled capture and release of dichloromethane (DCM) droplets on dodecylbenzenesulfonate-doped polypyrrole (PPy(DBS)) surfaces in an aqueous environment. The droplets captured on oxidized PPy(DBS) surfaces were released on-demand via a reduction process at ∼0.9 V, with controlled release time and droplet morphology. The release time of an entire droplet (2 ± 1 µL) was proportional to the thickness of the PPy(DBS) coating, increasing from 11.5 to 26.3 s for thicknesses ranging from 0.6 to 5.1 µm. The droplet-release time was also affected by the redox voltages, and among the tested redox voltages, the fastest release was achieved at -0.9/0.1 V. The PPy(DBS) surfaces with larger thicknesses were more durable for the droplet capture and release. The droplets were more rapidly released from PPy(DBS) surfaces with increased surface roughness ratios, such as 6.0 s on a micropillared surface and 10.3 s on a meshed surface, as compared to 14.6 s on the 1.8 µm thick PPy(DBS) surfaces coated on frosted-glass substrates (i.e., with random microstructures). The release of a single droplet was achieved by increasing the underwater oleophobicity of PPy(DBS) surface via O2 plasma treatment.