Asymmetric contact-induced selective doping of CVD-grown bilayer WS2 and its application in high-performance photodetection with an ultralow dark current.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) are excellent candidates for high-performance optoelectronics due to their high carrier mobility, air stability and strong optical absorption. However, photodetectors made with monolayer TMDs often exhibit a high dark current, and thus, there is a scope for further improvement. Herein, we developed a 2D bilayer tungsten disulfide (WS2) based photodetector (PD) with asymmetric contacts that exhibits an exceptionally low dark current and high specific detectivity. High-quality and large-area monolayer and bilayer WS2 flakes were synthesized using a thermal chemical vapor deposition system. Compared to conventional symmetric contact electrodes, utilizing metal electrodes with higher and lower work functions relative to bilayer WS2 aids in achieving asymmetric lateral doping in the WS2 flakes. This doping asymmetry was confirmed through the photoluminescence spectral profile and Raman mapping analysis. With the asymmetric contacts on bilayer WS2, we find evidence of selective doping of electrons and holes near the Ti and Au contacts, respectively, while the WS2 region away from the contacts remains intrinsic. When compared with the symmetric contact case, the dark current in the WS2 PD with asymmetric (Au, Ti) contact decreases by an order of magnitude under reverse bias with a concomitant increase in the photocurrent, resulting in an improved on/off ratio of ∼105 and overall improved device performance under identical illumination conditions. We explained this improved performance based on the energy band alignment showing a unidirectional charge flow under light illumination. Our results indicate that the planar device structure and compatibility with current nanofabrication technologies can facilitate its integration into advanced chips for futuristic low-power optoelectronic and nanophotonic applications.

Role of Diffusion Tensor Imaging in Early Diagnosis and Characterization of Movement Disorders.

BACKGROUND: Symptoms of movement disorders in early stages are similar, which makes definite diagnosis difficult. Hence this study was conducted to explore the role of diffusion tensor imaging (DTI) in enhancing the early diagnosis and characterization of movement disorders. METHODOLOGY: A cross-sectional study was conducted including 60 subjects. All of them were reviewed using conventional magnetic resonance imaging (MRI) and movement disorder DTI protocol. Commercially available software was used to produce fractional anisotropy (FA) maps. Post-processing 3D reconstruction was done to obtain tractograms. Both single and multiple regions of interest (ROIs) were selected for tractography in the pons, midbrain, substantia nigra (SN) and cerebellum. MRI and DTI images were interpreted and correlated with confirmatory diagnosis. RESULTS: According to DTI diagnosis, out of the 30 cases, 28 had movement disorders. Among cases, 36.67% had Parkinson's disease (PD), 23.33% had progressive supranuclear palsy (PSP), 16.67% had essential tremor, 13.33% had multi-system atrophy (MSA) C, and 3.33% had MSA P. DTI correctly classified all cases with PD and PSP. All cases with long disease duration and 88.24% of cases with short disease duration were also correctly classified. A statistically significant difference was observed in the proportion of diagnosis between DTI and conventional MRI. CONCLUSION: DTI has high sensitivity and specificity for the diagnosis of movement disorders. It is capable of early diagnosis of movement disorders and also differentiating and subcategorizing them.

Printed MoSe2/GaAs Photodetector Enabling Ultrafast and Broadband Photodetection up to 1.5 µm.

The development of high-performance and low-cost photodetectors (PDs) capable of detecting a broad range of wavelengths, from ultraviolet (UV) to near-infrared (NIR), is crucial for applications in sensing, imaging, and communication systems. This work presents a novel approach for printing a broadband PD based on a heterostructure of two-dimensional (2D) molybdenum diselenide (MoSe2) and gallium arsenide (GaAs). The fabrication process involves a precise technique to print MoSe2 nanoflower (NF) ink onto a prepatterned GaAs substrate. The resulting heterostructure exhibits unique properties, leveraging the exceptional electronic and optical characteristics of both GaAs and 2D MoSe2. The fabricated PD achieves an astounding on-off ratio of ∼105 at 5 V bias while demonstrating an exceptional on-off ratio of ∼104 at 0 V. The depletion region between GaAs and MoSe2 facilitates efficient charge generation and separation and collection of photogenerated carriers. This significantly improves the performance of the PD, resulting in a notably high responsivity across the spectrum. The peak responsivity of the device is 5.25 A/W at 5 V bias under 808 nm laser excitation, which is more than an order of magnitude higher than that of any commercial NIR PDs. Furthermore, the device demonstrates an exceptional responsivity of 0.36 A/W under an external bias of 0 V. The printing technology used here offers several advantages including simplicity, scalability, and compatibility with large-scale production. Additionally, it enables precise control over the placement and integration of the MoSe2 NF onto the GaAs substrate, ensuring uniformity and reliability in device performance. The exceptional responsivity across a broad spectral range (360-1550 nm) and the success of the printing technique make our MoSe2/GaAs heterostructure PD promising for future low-cost and efficient optoelectronic devices.

A fully printed ultrafast Si/WS2 quantum dot photodetector with very high responsivity over the UV to near-infrared region.

Two-dimensional (2D) semiconducting material-based photodetectors (PDs) with high responsivity and fast photo-response are of great interest for various applications such as optical communications, biomedical imaging, security surveillance, environmental monitoring, etc. Additive manufacturing such as 2D printing is a potentially less cumbersome and cost-effective alternative to conventional microdevice fabrication processes used in the production of PDs. Here, we have fabricated a Si/WS2 quantum dot-based heterostructure PD with a very short electrode gap of 40 µm by a simple printing process. The printed p-Si/n-WS2 PD shows an excellent photo-to-dark current ratio of 5121 under 405 nm illumination (23.8 mW cm-2). The printed photodetector exhibits a peak responsivity of 126 A W-1 and a peak detectivity of 9.24 × 1012 Jones over a very broad wavelength range (300-1100 nm), which is much superior to commercial Si PDs. A high external quantum efficiency of 3.9 × 104% and an ultrafast photoresponse (7.8 µs rise time and 9.5 µs fall time) make the device an attractive candidate as an efficient photodetector. The origin of high-performance photodetection is traced to a nearly defect-free interface at the heterojunction, leading to highly efficient charge separation and high photocurrent. Finally, the 2D-printed device exhibits good photodetection even in self-powered conditions, which is very attractive.

Two-Dimensional Transition Metal Dichalcogenide Based Biosensors: From Fundamentals to Healthcare Applications.

There has been an exponential surge in reports on two-dimensional (2D) materials ever since the discovery of graphene in 2004. Transition metal dichalcogenides (TMDs) are a class of 2D materials where weak van der Waals force binds individual covalently bonded X-M-X layers (where M is the transition metal and X is the chalcogen), making layer-controlled synthesis possible. These individual building blocks (single-layer TMDs) transition from indirect to direct band gaps and have fascinating optical and electronic properties. Layer-dependent opto-electrical properties, along with the existence of finite band gaps, make single-layer TMDs superior to the well-known graphene that paves the way for their applications in many areas. Ultra-fast response, high on/off ratio, planar structure, low operational voltage, wafer scale synthesis capabilities, high surface-to-volume ratio, and compatibility with standard fabrication processes makes TMDs ideal candidates to replace conventional semiconductors, such as silicon, etc., in the new-age electrical, electronic, and opto-electronic devices. Besides, TMDs can be potentially utilized in single molecular sensing for early detection of different biomarkers, gas sensors, photodetector, and catalytic applications. The impact of COVID-19 has given rise to an upsurge in demand for biosensors with real-time detection capabilities. TMDs as active or supporting biosensing elements exhibit potential for real-time detection of single biomarkers and, hence, show promise in the development of point-of-care healthcare devices. In this review, we provide a historical survey of 2D TMD-based biosensors for the detection of bio analytes ranging from bacteria, viruses, and whole cells to molecular biomarkers via optical, electronic, and electrochemical sensing mechanisms. Current approaches and the latest developments in the study of healthcare devices using 2D TMDs are discussed. Additionally, this review presents an overview of the challenges in the area and discusses the future perspective of 2D TMDs in the field of biosensing for healthcare devices.

Quantitative Detection of Cathepsin B Activity in Neutral pH Buffers Using Gold Microelectrode Arrays: Toward Direct Multiplex Analyses of Extracellular Proteases in Human Serum.

Proteases are critical signaling molecules and prognostic biomarkers for many diseases including cancer. There is a strong demand for multiplex bioanalytical techniques that can rapidly detect the activity of extracellular proteases with high sensitivity and specificity. This study demonstrates an activity-based electrochemical biosensor of a 3 × 3 gold microelectrode array for the detection of cathepsin B activity in human serum diluted in a neutral buffer. Proteolysis of ferrocene-labeled peptide substrates functionalized on 200 × 200 µm microelectrodes is measured simultaneously over the nine channels by AC voltammetry. The protease activity is represented by the inverse of the exponential decay time constant (1/τ), which equals to (kcat/KM)[CB] based on the Michaelis-Menten model. An enhanced activity of the recombinant human cathepsin B (rhCB) is observed in a low-ionic-strength phosphate buffer at pH = 7.4, giving a very low limit of detection of 8.49 × 10-4 s-1 for activity and 57.1 pM for the active rhCB concentration that is comparable to affinity-based enzyme-linked immunosorbent assay (ELISA). The cathepsin B presented in the human serum sample is validated by ELISA, which mainly detects the inactive proenzyme, while the electrochemical biosensor specifically measures the active cathepsin B and shows significantly higher decay rates when rhCB and human serum are activated. Analyses of the kinetic electrochemical measurements with spiked active cathepsin B in human serum provide further assessment of the protease activity in the complex sample. This study lays the foundation to develop the gold microelectrode array into a multiplex biosensor for rapid detection of the activity of extracellular proteases toward cancer diagnosis and treatment assessment.

Effect of 150 MeV protons on carbon nanotubes for fabrication of a radiation detector.

High energy and high flux protons are used in proton therapy and the impact of proton radiation is a major reliability concern for electronics and solar cells in low earth orbit as well as in the trapped belts. Carbon nanotubes (CNTs), due to their unique characteristics, have been considered for the construction of proton and other radiation sensors. Here, a single wall CNT based proton sensor was fabricated on FR4 substrate and its response to 150 MeV proton irradiation was studied. The change in the resistance of the nanotubes upon irradiation is exploited as the sensing mechanism and the sensor shows good sensitivity to proton radiation. Proton radiation induces dissociation of ambient oxygen, followed by the adsorption of oxygen species on the nanotube surface, which influences its electrical characteristics. Since the nanotube film is thin and the 150 MeV protons are expected to penetrate into and interact with the substrate, control experiments were conducted to study the impact on FR4 substrate without the nanotubes. The dielectric loss tangent or dissipation factor of FR4 increases after irradiation due to an increase in the cross-linking of the resin arising from the degradation of the polymer network.

Methodologies for Fabricating Flexible Supercapacitors.

The spread of wearable and flexible electronics devices has been accelerating in recent years for a wide range of applications. Development of an appropriate flexible power source to operate these flexible devices is a key challenge. Supercapacitors are attractive for powering portable lightweight consumer devices due to their long cycle stability, fast charge-discharge cycle, outstanding power density, wide operating temperatures and safety. Much effort has been devoted to ensure high mechanical and electrochemical stability upon bending, folding or stretching and to develop flexible electrodes, substrates and overall geometrically-flexible structures. Supercapacitors have attracted considerable attention and shown many applications on various scales. In this review, we focus on flexible structural design under six categories: paper-like, textile-like, wire-like, origami, biomimetics based design and micro-supercapacitors. Finally, we present our perspective of flexible supercapacitors and emphasize current technical difficulties to stimulate further research.

Printable Gel Polymer Electrolytes for Solid-State Printed Supercapacitors.

Supercapacitors prepared by printing allow a simple manufacturing process, easy customization, high material efficiency and wide substrate compatibility. While printable active layers have been widely studied, printable electrolytes have not been thoroughly investigated despite their importance. A printable electrolyte should not only have high ionic conductivity, but also proper viscosity, small particle size and chemical stability. Here, gel-polymer electrolytes (GPE) that are compatible with printing were developed and their electrochemical performance was analyzed. Five GPE formulations based on various polymer-conductive substance combinations were investigated. Among them, GPE made of polyvinylidene difluoride (PVDF) polymer matrix and LiClO4 conductive substance exhibited the best electrochemical performance, with a gravimetric capacitance of 176.4 F/g and areal capacitance of 152.7 mF/cm2 at a potential scan rate of 10 mV/s. The in-depth study of the in-plane solid-state supercapacitors based on various printed GPEs suggests that printable electrolytes provide desirable attributes for high-performance printed energy devices such as supercapacitors, batteries, fuel cells and dye-sensitized solar cells.

A nanoscale vacuum field emission gated diode with an umbrella cathode.

A nanoscale field emission vacuum channel gated diode structure is proposed and a tungsten cathode with an umbrella-like geometry and sharp vertical edge is fabricated. The edge of the suspended cathode becomes the field emission surface. Unlike in the traditional transistor with the gate typically located between the source and the drain, the bottom silicon plate becomes the gate here and the anode terminal is located between the umbrella cathode and the gate. The fabricated devices show excellent diode characteristics and the gated diode structure is attractive for extremely low gate leakage.

Hexagonal Boron Nitride for Sulfur Corrosion Inhibition.

Corrosion by sulfur compounds is a long-standing challenge in many engineering applications. Specifically, designing a coating that protects metals from both abiotic and biotic forms of sulfur corrosion remains an elusive goal. Here we report that atomically thin layers (∼4) of hexagonal boron nitride (hBN) act as a protective coating to inhibit corrosion of the underlying copper (Cu) surfaces (∼6-7-fold lower corrosion than bare Cu) in abiotic (sulfuric acid and sodium sulfide) and biotic (sulfate-reducing bacteria medium) environments. The corrosion resistance of hBN is attributed to its outstanding barrier properties to the corrosive species in diverse environments of sulfur compounds. Increasing the number of atomic layers did not necessarily improve the corrosion protection mechanisms. Instead, multilayers of hBN were found to upregulate the adhesion genes in Desulfovibrio alaskensis G20 cells, promote cell adhesion and biofilm growth, and lower the protection against biogenic sulfide attack when compared to the few layers of hBN. Our findings confirm hBN as the thinnest coating to resist diverse forms of sulfur corrosion.

Simultaneous, multiplex quantification of protease activities using a gold microelectrode array.

Proteases are a large family of enzymes involved in many important biological processes. Quantitative detection of the activity profile of specific target proteases is in high demand for the diagnosis and monitoring of diseases such as cancers. This study demonstrates the fabrication and characterization of an individually addressable 3 × 3 Au microelectrode array for rapid, multiplex detection of cathepsin B activity based on a simple electrochemical method. The nine individual microelectrodes in the array show highly consistent cyclic voltammetric signals in Au surface cleaning experiments and detecting benchmark redox species in solution. The individual Au microelectrodes are further selectively functionalized with specific ferrocene-labeled peptide molecules which serve as the cognate substrates for the target proteases. Consistent proteolytic kinetics are measured by monitoring the decay of the AC voltammetry signal from the ferrocene label as the peptide molecules are cleaved by cathepsin B. Accurate activity of cathepsin B is derived with an improved fitting algorithm. Simultaneous detection of the proteolysis of cathepsin B on the microelectrode array functionalized with three different hexapeptides is demonstrated, showing the potential of this sensor platform for rapid detection of the activity profiles of multiple proteases in various diseases including many forms of cancer.

All 3D-Printed Flexible ZnO UV Photodetector on an Ultraflat Substrate.

An all three-dimensional (3D)-printed flexible ZnO ultraviolet (UV) photodetector is demonstrated, where the 3D-printing method is used not only for the electrode and photosensitive material but also for creating a substrate. An ultraflat and flexible substrate capable of serving as the backbone layer is developed using a water-dissolvable polymer layer for surface planarization. A two-layered printing followed by surface treatment is demonstrated for the substrate preparation. As mechanical support but flexible, a thick and sparse thermoplastic polyurethane layer is printed. On its surface, a thin and dense poly(vinyl alcohol) (PVA) is then printed. A precise control of PVA reflow using a microwater droplet results in a flexible and extremely uniform substrate. A Cu-Ag nanowire network is directly 3D printed on the flexible substrate for the conducting layer, followed by ZnO for the photosensitive material. Unlike the planar two-dimensional printing that provides thin films, 3D printing allows the electrode to have a step height, which can be made like a dam to accommodate a thick film of ZnO. Photosensitivity as a function of various ZnO thickness values was investigated to establish an optimal thickness for UV response. The device was also tested in natural sunlight along with stability and reliability.

On-Demand Printing of Wearable Thermotherapy Pad.

Thermotherapy is an effective method for pain relief, recovery from injury, and general healthcare. The ordinary heat pad used for thermotherapy at home is not usually tailored to the individual but supplied in a few different pre-fixed sizes and shapes for mass marketing. A customized wearable heat pad often requires expert support. Herein, an instant, custom-fit, and on-demand heat pad for thermotherapy is demonstrated. The heater is directly printed using silver nanoparticle ink on an off-the-shelf medical grade tape by inkjet technology. By coating the tape with silica nanoparticles as ink-absorbing layer and chloride ions as chemical sintering agent, stable heater patterns are printed without the need for subsequent high temperature sintering process. A 3D scanner is used to acquire body information, and a customized heater is produced using the information. The printed heat pad is attached to the shoulder and the effect of thermotherapy is verified objectively through electroencephalography and subjectively through survey. This printed heat pad produced by simple and low-cost fabrication provides wearable medical devices for personal thermotherapy.

Integrating Carbon Nanomaterials with Metals for Bio-sensing Applications.

Age structure in most developed countries is changing fast as the average lifespan is increasing significantly, calling for solutions to provide improved treatments for age-related neurological diseases and disorders. In order to address these problems, a reliable way of recording information about neurotransmitters from in vitro and in vivo applications is needed to better understand neurological diseases and disorders as well as currently used treatments. Likewise, recent developments in medicine, especially with the opioid crisis, are demanding a swift move to personalized medicine to administer patient needs rather than population-wide averages. In order to enable the so-called personalized medicine, it is necessary to be able to do measurements in vivo and in real time. These actions require sensitive and selective detection of different analytes from very demanding environments. Current state-of-the-art materials are unable to provide sensitive and selective detection of neurotransmitters as well as the required time resolution needed for drug molecules at a reasonable cost. To meet these challenges, we have utilized different metals to grow carbon nanomaterials and applied them for sensing applications showing that there are clear differences in their electrochemical properties based on the selected catalyst metal. Additionally, we have combined atomistic simulations to support optimizing materials for experiments and to gain further understanding of the atomistic level reactions between different analytes and the sensor surface. With carbon nanostructures grown from Ni and Al + Co + Fe hybrid, we can detect dopamine, ascorbic acid, and uric acid simultaneously. On the other hand, nanostructures grown from platinum provide a feasible platform for detection of H2O2 making them suitable candidates for enzymatic biosensors for detection of glutamate, for example. Tetrahedral amorphous carbon electrodes have an ability to detect morphine, paracetamol, tramadol, and O-desmethyltramadol. With carbon nanomaterial-based sensors, it is possible to reach metal-like properties in sensing applications using only a fraction of the metal as seed for the material growth. We have also seen that by using nanodiamonds as growth catalyst for carbon nanofibers, it is not possible to detect dopamine and ascorbic acid simultaneously, although the morphology of the resulting nanofibers is similar to the ones grown using Ni. This further indicates the importance of the metal selection for specific applications. However, Ni as a continuous layer or as separate islands does not provide adequate performance. Thus, it appears that metal nanoparticles combined with fiber-like morphology are needed for optimized sensor performance for neurotransmitter detection. This opens up a new research approach of application-specific nanomaterials, where carefully selected metals are integrated with carbon nanomaterials to match the needs of the sensing application in question.

Carbon Nanotube Based γ Ray Detector.

A single walled carbon nanotube (SWCNT) based γ ray detector is demonstrated without a conventional scintillation mechanism. The change in the conductance of a two terminal SWCNT resistor in response to γ ray exposure is exploited as a sensing mechanism. Radiation-induced ambient oxygen dissociation and subsequent adsorption of oxygen species on the SWCNT surface alter its electrical properties. The responses to the total dose and dose rate are investigated along with the sensing mechanism. The detector showed good sensitivity to γ ray and a capability to distinguish radiation dose rates ranging from 2.4 to 16.4 R/min.

Electrochemical Activity Assay for Protease Analysis Using Carbon Nanofiber Nanoelectrode Arrays.

There is a strong demand for bioanalytical techniques to rapidly detect protease activities with high sensitivity and high specificity. This study reports an activity-based electrochemical method toward this goal. Nanoelectrode arrays (NEAs) fabricated with embedded vertically aligned carbon nanofibers (VACNFs) are functionalized with specific peptide substrates containing a ferrocene (Fc) tag. The kinetic proteolysis curves are measured with continuously repeated ac voltammetry, from which the catalytic activity is derived as the inverse of the exponential decay time constant based on a heterogeneous Michaelis-Menten model. Comparison of three peptide substrates with different lengths reveals that the hexapeptide H2N-(CH2)4-CO-Pro-Leu-Arg-Phe-Gly-Ala-NH-CH2-Fc is the optimal probe for cathepsin B. The activity strongly depends on temperature and is the highest around the body temperature. With the optimized peptide substrate and measuring conditions, the limit of detection of cathepsin B activity and concentration can reach 2.49 × 10-4 s-1 and 0.32 nM, respectively. The peptide substrates show high specificity to the cognate proteases, with negligible cross-reactions among three cancer-related proteases cathepsin B, ADAM10, and ADAM17. This electrochemical method can be developed into multiplex chips for rapid profiling of protease activities in cancer diagnosis and treatment monitoring.

Vertical Silicon Nanowire Thermoelectric Modules with Enhanced Thermoelectric Properties.

Thermoelectric modules based on silicon nanowires (Si-NWs) have recently attracted significant attention as they show an improved thermoelectric efficiency due to a decrease in thermal conductivity. Here, we adopt a top-down fabrication method to dramatically reduce the thermal conductivity of vertical Si-NWs. The thermal conductivity of a vertical Si-NW is significantly suppressed with an increasing surface roughness, decreasing diameter, and increasing doping concentration. This large suppression is caused by enhanced phonon scattering, which depends on the phonon wavelength. The boron- and phosphorus-doped rough Si-NWs with a diameter of 200 nm and surface roughness of 6.88 nm show the lowest thermal conductivity of 10.1 and 14.8 W·m-1·K-1, respectively, which are 5.1- and 3.6-fold lower than that of a smooth intrinsic nanowire and 14.8- and 10.1-fold lower than that of bulk silicon. A thermoelectric module was fabricated using this doped rough Si-NW array, and its thermoelectric performance is compared with previously reported Si-NW modules. The fabricated module exhibits an excellent performance with an open circuit voltage of 216.8 mV·cm-2 and a maximum power of 3.74 µW·cm-2 under a temperature difference of 180 K, the highest reported for Si-NW thermoelectric modules.

Annealing effect on UV-illuminated recovery in gas response of graphene-based NO2 sensors.

The response and recovery of a graphene-based sensor for nitrogen dioxide (NO2) sensing is improved by a combination of two treatments including rapid thermal annealing (RTA) of graphene and UV illumination during the pump down period. A two-dimensional monolayer graphene grown by chemical vapor deposition was transferred to an arc-shape electrode and subsequently heated at temperatures from 200 to 400 °C for 1 min in N2 atmosphere by RTA to eliminate the chemical residues on the graphene generated in the transfer process. The effect of RTA and poly(methyl methacrylate) (PMMA) residues was investigated using Raman spectroscopy. The shift of the G and 2D bands could be due to graphene suffering from compressive strain and hole doping from the substrate enhanced by the RTA treatment. The hole doping effect was also observed from Hall measurements. Atomic force microscopy images confirm the PMMA residues and surface roughness reduction by the RTA treatment. Annealing at 300 °C enhances the NO2 sensing response at 1 ppm by 4 times compared to the pristine graphene without RTA. Full recovery of the sensor to the initial baseline could be achieved by the adjustment of UV illumination time.