Intercalation of Zinc Monochloride Cations by Deep Eutectic Solvents for High-Performance Rechargeable Non-aqueous Zinc Ion Batteries.

Zinc ion batteries have been extensively studied with an aqueous electrolyte system. However, the batteries suffer from a limited potential window, gas evolution, cathode dissolution, and dendrite formation on the anode. Considering these limitations, we developed an alternative electrolyte system based on deep eutectic solvents (DESs) because of their low cost, high stability, biodegradability, and non-flammability, making them optimal candidates for sustainable batteries. The DES electrolyte enables reversible Zn plating/stripping and effectively suppresses zinc dendrite formation. Furthermore, in-depth characterizations reveal that the energy storage mechanism can be attributed to [ZnCl]+ ion intercalation and the intermediate complex ion plays a pivotal role in electrochemical reactions, which deliver a high reversible capacity of 310 mAh g-1 at 0.1 A g-1and long-term stability (167 mAh g-1 at a current density of 0.3 A g-1 after 300 cycles, Coulombic efficiency: ∼98%). Overall, this work represents our new finding in rechargeable batteries with the DES electrolyte.

Design of Core-Shell Quantum Dots-3D WS2 Nanowall Hybrid Nanostructures with High-Performance Bifunctional Sensing Applications.

Transition metal dichalcogenides (TMDCs) have recently attracted a tremendous amount of attention owing to their superior optical and electrical properties as well as the interesting and various nanostructures that are created by different synthesis processes. However, the atomic thickness of TMDCs limits the light absorption and results in the weak performance of optoelectronic devices, such as photodetectors. Here, we demonstrate the approach to increase the surface area of TMDCs by a one-step synthesis process of TMDC nanowalls from WOx into three-dimensional (3D) WS2 nanowalls. By utilizing a rapid heating and rapid cooling process, the formation of 3D nanowalls with a height of approximately 150 nm standing perpendicularly on top of the substrate can be achieved. The combination of core-shell colloidal quantum dots (QDs) with three different emission wavelengths and 3D WS2 nanowalls further improves the performance of WS2-based photodetector devices, including a photocurrent enhancement of 320-470% and shorter response time. The significant results of the core-shell QD-WS2 hybrid devices can be contributed by the high nonradiative energy transfer efficiency between core-shell QDs and the nanostructured material, which is caused by the spectral overlap between the emission of core-shell QDs and the absorption of WS2. Besides, outstanding NO2 gas-sensing performance of core-shell QDs/WS2 devices can be achieved with an extremely low detection limit of 50 ppb and a fast response time of 26.8 s because of local p-n junctions generated by p-type 3D WS2 nanowalls and n-type core-shell CdSe-ZnS QDs. Our work successfully reveals the energy transfer phenomenon in core-shell QD-WS2 hybrid devices and shows great potential in commercial multifunctional sensing applications.

Three-Dimensional Molybdenum Diselenide Helical Nanorod Arrays for High-Performance Aluminum-Ion Batteries.

The rechargeable aluminum-ion battery (AIB) is a promising candidate for next-generation high-performance batteries, but its cathode materials require more development to improve their capacity and cycling life. We have demonstrated the growth of MoSe2 three-dimensional helical nanorod arrays on a polyimide substrate by the deposition of Mo helical nanorod arrays followed by a low-temperature plasma-assisted selenization process to form novel cathodes for AIBs. The binder-free 3D MoSe2-based AIB shows a high specific capacity of 753 mAh g-1 at a current density of 0.3 A g-1 and can maintain a high specific capacity of 138 mAh g-1 at a current density of 5 A g-1 with 10 000 cycles. Ex situ Raman, XPS, and TEM characterization results of the electrodes under different states confirm the reversible alloying conversion and intercalation hybrid mechanism during the discharge and charge cycles. All possible chemical reactions were proposed by the electrochemical curves and characterization. Further exploratory works on interdigital flexible AIBs and stretchable AIBs were demonstrated, exhibiting a steady output capacity under different bending and stretching states. This method provides a controllable strategy for selenide nanostructure-based AIBs for use in future applications of energy-storage devices in flexible and wearable electronics.

Nanoprobing of MoS2 by Synchrotron Radiation When van der Waals Epitaxy Is Locally Invalid.

In this work, we demonstrated nano-scaled Laue diffractions by a focused polychromatic synchrotron radiation beam to discover what happens in MoS2 when van der Waals epitaxy is locally invalid. A stronger exciton recombination with a local charge depletion in the density of 1 × 1013 cm-2, extrapolated by Raman scattering and photoluminescence, occurs in grains, which exhibits a preferred orientation of 30° rotation with respect to the c-plane of a sapphire substrate. Else, the charge doping and trion recombination dominate instead. In addition to the breakthrough in extrapolating mesoscopic crystallographic characteristics, this work opens the feasibility to manipulate charge density by the selection of the substrate-induced disturbances without external treatment and doping. Practically, the 30° rotated orientation in bilayer MoS2 films is promoted on inclined facets in the patterned sapphire substrate, which exhibits a periodic array of charge depletion of about 1.65 × 1013 cm-2. The built-in manipulation of carrier concentrations could be a potential candidate to lateral and large-area electronics based on 2D materials.

High-Performance Rechargeable Aluminum-Selenium Battery with a New Deep Eutectic Solvent Electrolyte: Thiourea-AlCl3.

Aluminum-sulfur batteries (ASBs) have attracted substantial interest due to their high theoretical specific energy density, low cost, and environmental friendliness, while the traditional sulfur cathode and ionic liquid have very fast capacity decay, limiting cycling performance because of the sluggishly electrochemical reaction and side reactions with the electrolyte. Herein, we demonstrate, for the first time, excellent rechargeable aluminum-selenium batteries (ASeBs) using a new deep eutectic solvent, thiourea-AlCl3, as an electrolyte and Se nanowires grown directly on a flexible carbon cloth substrate (Se NWs@CC) by a low-temperature selenization process as a cathode. Selenium (Se) is a chemical analogue of sulfur with higher electronic conductivity and lower ionization potential that can improve the battery kinetics on the sluggishly electrochemical reaction and the reduction of the polarization where the thiourea-AlCl3 electrolyte can stabilize the side reaction during the reversible conversion reaction of Al-Se alloying processes during the charge-discharge process, yielding a high specific capacity of 260 mAh g-1 at 50 mA g-1 and a long cycling life of 100 times with a high Coulombic efficiency of nearly 93% at 100 mA g-1. The working mechanism based on the reversible conversion reaction of the Al-Se alloying processes, confirmed by the ex situ Raman, XRD, and XPS measurements, was proposed. This work provides new insights into the development of rechargeable aluminum-chalcogenide (S, Se, and Te) batteries.

Three-Dimensional CuO/TiO2 Hybrid Nanorod Arrays Prepared by Electrodeposition in AAO Membranes as an Excellent Fenton-Like Photocatalyst for Dye Degradation.

Three-dimensional (3D) CuO/TiO2 hybrid heterostructure nanorod arrays (NRs) with noble-metal-free composition, fabricated by template-assisted low-cost processes, were used as the photo-Fenton-like catalyst for dye degradation. Here, CuO NRs were deposited into anodic aluminum oxide templates by electrodeposition method annealed at various temperatures, followed by deposition of TiO2 thin films through E-gun evaporation, resulting in the formation of CuO/TiO2 p-n heterojunction. The distribution of elements and compositions of the CuO/TiO2 p-n heterojunction were analyzed by EDS mapping and EELS profiles, respectively. In the presence of H2O2, CuO/TiO2 hybrid structure performed more efficiently than CuO NRs for Rhodamine B degradation under the irradiation of 500-W mercury-xenon arc lamp. This study demonstrated the effect of length of CuO NRs, on the photo-degradation performance of CuO NRs as well as CuO/TiO2 heterostructure. The optimized CuO/TiO2 hybrid NR array structure exhibited the highest photo-degradation activity, and the mechanism and role of photo-Fenton acting as the catalyst in photo-degradation of dye was also investigated.

Seeing pressure in color based on integration of highly sensitive pressure sensor and emission tunable light emitting diode.

We demonstrate a highly sensitive, low-cost, environmental-friendly pressure sensor derived from a wool-based pressure sensor with wide pressure sensing range using wool bricks embedded with a Ag nano-wires. The easy fabrication and light weight allow portable and wearable device applications. Wth the integration of a light-emitting diode possessing multi-wavelength emission, we illustrate a hybrid multi-functional LED-integrated pressure sensor that is able to convert different applied pressures to light emission with different wavelengths. Due to the high sensitivity of the pressure sensor, the demonstration of acoustic signal detection has also been presented using sound of a metronome and a speaker playing a song. This multi-functional pressure sensor can be implemented to technologies such as smart lighting, health care, visible light communication (VLC), and other internet of things (IoT) applications.

3D CoMoSe4 Nanosheet Arrays Converted Directly from Hydrothermally Processed CoMoO4 Nanosheet Arrays by Plasma-Assisted Selenization Process Toward Excellent Anode Material in Sodium-Ion Battery.

In this work, three-dimensional (3D) CoMoSe4 nanosheet arrays on network fibers of a carbon cloth denoted as CoMoSe4@C converted directly from CoMoO4 nanosheet arrays prepared by a hydrothermal process followed by the plasma-assisted selenization at a low temperature of 450 °C as an anode for sodium-ion battery (SIB) were demonstrated for the first time. With the plasma-assisted treatment on the selenization process, oxygen (O) atoms can be replaced by selenium (Se) atoms without the degradation on morphology at a low selenization temperature of 450 °C. Owing to the high specific surface area from the well-defined 3D structure, high electron conductivity, and bi-metal electrochemical activity, the superior performance with a large sodium-ion storage of 475 mA h g-1 under 0.5-3 V potential range at 0.1 A g-1 was accomplished by using this CoMoSe4@C as the electrode. Additionally, the capacity retention was well maintained over 80 % from the second cycle, exhibiting a satisfied capacity of 301 mA h g-1 even after 50 cycles. The work delivered a new approach to prepare a binary transition metallic selenide and definitely enriches the possibilities for promising anode materials in SIBs with high performances.

An indoor light-activated 3D cone-shaped MoS2 bilayer-based NO gas sensor with PPb-level detection at room-temperature.

Utilization of light to boost the performance of gas sensors allows us to operate sensor devices at room temperature. Here, we, for the first time, demonstrated an indoor light-activated 3D cone-shaped MoS2 bilayer-based NO gas sensor with ppb-level detection operated at room-temperature. Large-area cone-shaped (CS)-MoS2 bilayers were grown by depositing 2 nm-thick MoO3 layers on a 2'' three-dimensional (3D) cone-patterned sapphire substrate (CPSS) followed by a sulfurization process via chemical vapor deposition. Because the exposed area of MoS2 bilayers is increased by 30%, the CS-MoS2 gas sensor (GS) demonstrated excellent performance with a response of ∼470% and a fast response time of ∼25 s after exposure to 1 ppm of NO gas illuminated by ultraviolet (UV) light with a wavelength of 365 nm. Such extraordinary performance at room temperature is attributed to the enhanced light absorption because of the light scattering effect caused by the 3D configuration and photo-desorption induced by UV illumination. For NO concentrations ranging from 2 ppm down to 0.06 ppm, the CS-MoS2 GS demonstrated a stable sensing behavior with a high response and fast response time (470% and 25 s at 2 ppm NO) because of the light absorption enhanced by the 3D structure and photo-desorption under constant UV illumination. The CS-MoS2 GS exhibits a high sensitivity (∼189.2 R% ppm-1), allowing the detection of NO gas at 0.06 ppm in 130 s. In addition, the 3D cone-shaped structure prolonged the presence of sulfur vapor around MoO3, allowing MoO3 to react with sulfur completely. Furthermore, the CS-MoS2 GS using an indoor lighting to detect NO gas at room temperature was demonstrated for the first time where the CS-MoS2 GS exhibits a stable cycling behavior with a high response (165% at 1 ppm NO) in 50 s; for concentration as low as ∼0.06 ppm, the response of ∼75% in 150 s can be achieved.

Environmentally and Mechanically Stable Selenium 1D/2D Hybrid Structures for Broad-Range Photoresponse from Ultraviolet to Infrared Wavelengths.

Selenium (Se) is one of the potential candidates as photodetector because of its outstanding properties such as high photoconductivity (∼8 × 104 S cm-1), piezoelectricity, thermoelectricity, and nonlinear optical responses. Solution phase synthesis becomes an efficient way to produce Se, but a contamination issue that could deteriorate the electric characteristic of Se should be taken into account. In this work, a facile, controllable approach of synthesizing Se nanowires (NWs)/films via a plasma-assisted growth process was demonstrated at the low substrate temperature of 100 °C. The detailed formation mechanisms of nanowires arrays to thin films at different plasma powers were investigated. Moreover, indium (In) layer was used to enhance the adhesive strength with 50% improvement on a SiO2/Si substrate by mechanical interlocking and surface alloying between Se and In layers, indicating great tolerance for mechanical stress for future wearable devices applications. Furthermore, the direct growth of Se NWs/films on a poly(ethylene terephthalate) substrate was demonstrated, exhibiting a visible to broad infrared detection ranges from 405 to 1555 nm with a high on/off ratio of ∼700 as well as the fast response time less than 25 ms. In addition, the devices exhibited fascinating stability in the atmosphere over one month.

Pressure Welding of Silver Nanowires Networks at Room Temperature as Transparent Electrodes for Efficient Organic Light-Emitting Diodes.

In this work, polymethylmethacrylate (PMMA) as a superior mediate for the pressure welding of silver nanowires (Ag NWs) networks as transparent electrodes without any thermal treatment is demonstrated. After a pressing of 200 kg cm-2 , not only the sheet resistance but also the surface roughness of the PMMA-mediated Ag NWs networks decreases from 2.6 kΩ sq-1 to 34.3 Ω sq-1 and from 76.1 to 12.6 nm, respectively. On the other hand, high transparency of an average transmittance in the visible wavelengths of 93.5% together with a low haze value of 2.58% can be achieved. In terms of optoelectronic applications, the promising potential of the PMMA-mediated pressure-welded Ag NWs networks used as a transparent electrode in a green organic light-emitting diode (OLED) device is also demonstrated. In comparison with the OLED based on commercial tin-doped indium oxide electrode, the increments of power efficiency and external quantum efficiency (EQE) from 80.1 to 85.9 lm w-1 and 19.2% to 19.9% are demonstrated. In addition, the PMMA-mediated pressure welding succeeds in transferring Ag NWs networks to flexible polyethylene naphthalate and polyimide substrates with the sheet resistance of 42 and 91 Ω sq-1 after 10 000 times of bending, respectively.

Phase-Engineered Type-II Multimetal-Selenide Heterostructures toward Low-Power Consumption, Flexible, Transparent, and Wide-Spectrum Photoresponse Photodetectors.

Phase-engineered type-II metal-selenide heterostructures are demonstrated by directly selenizing indium-tin oxide to form multimetal selenides in a single step. The utilization of a plasma system to assist the selenization facilitates a low-temperature process, which results in large-area films with high uniformity. Compared to single-metal-selenide-based photodetectors, the multimetal-selenide photodetectors exhibit obviously improved performance, which can be attributed to the Schottky contact at the interface for tuning the carrier transport, as well as the type-II heterostructure that is beneficial for the separation of the electron-hole pairs. The multimetal-selenide photodetectors exhibit a response to light over a broad spectrum from UV to visible light with a high responsivity of 0.8 A W-1 and an on/off current ratio of up to 102 . Interestingly, all-transparent photodetectors are successfully produced in this work. Moreover, the possibility of fabricating devices on flexible substrates is also demonstrated with sustainable performance, high strain tolerance, and high durability during bending tests.

Phase-Engineered PtSe2 -Layered Films by a Plasma-Assisted Selenization Process toward All PtSe2 -Based Field Effect Transistor to Highly Sensitive, Flexible, and Wide-Spectrum Photoresponse Photodetectors.

The formation of PtSe2 -layered films is reported in a large area by the direct plasma-assisted selenization of Pt films at a low temperature, where temperatures, as low as 100 °C at the applied plasma power of 400 W can be achieved. As the thickness of the Pt film exceeds 5 nm, the PtSe2 -layered film (five monolayers) exhibits a metallic behavior. A clear p-type semiconducting behavior of the PtSe2 -layered film (≈trilayers) is observed with the average field effective mobility of 0.7 cm2 V-1 s-1 from back-gated transistor measurements as the thickness of the Pt film reaches below 2.5 nm. A full PtSe2 field effect transistor is demonstrated where the thinner PtSe2 , exhibiting a semiconducting behavior, is used as the channel material, and the thicker PtSe2 , exhibiting a metallic behavior, is used as an electrode, yielding an ohmic contact. Furthermore, photodetectors using a few PtSe2 -layered films as an adsorption layer synthesized at the low temperature on a flexible substrate exhibit a wide range of absorption and photoresponse with the highest photocurrent of 9 µA under the laser wavelength of 408 nm. In addition, the device can maintain a high photoresponse under a large bending stress and 1000 bending cycles.

Selection Role of Metal Oxides into Transition Metal Dichalcogenide Monolayers by a Direct Selenization Process.

Direct reduction of metal oxides into a few transition metal dichalcogenide (TMDCs) monolayers has been recently explored as an alternative method for large area and uniform deposition. However, not many studies have addressed the characteristics and requirement of the metal oxides into TMDCs by the selenization/sulfurization processes, yielding a wide range of outstanding properties to poor electrical characteristics with nonuniform films. The large difference implies that the process is yet not fully understood. In particular, the selenization/sulfurization at low temperature leads to poor crystallinity films with poor electrical performance, hindering its practical development. A common approach to improve the quality of the selenized/sulfurized films is by further increasing the process temperature, thus requiring additional transfer in order to explore the electrical properties. Here, we show that by finely tuning the quality of the predeposited oxide the selenization/sulfurization temperature can be largely decreased, avoiding major substrate damage and allowing direct device fabrication. The direct relationship between the role of selecting different metal oxides prepared by e-beam evaporation and reactive sputtering and their oxygen deficiency/vacancy leading to quality influence of TMDCs was investigated in detail. Because of its outstanding physical properties, the formation of tungsten diselenide (WSe2) from the reduction of tungsten oxide (WO x) was chosen as a model for proof of concept. By optimizing the process parameters and the selection of metal oxides, layered WSe2 films with controlled atomic thickness can be demonstrated. Interestingly, the domain size and electrical properties of the layered WSe2 films are highly affected by the quality of the metal oxides, for which the layered WSe2 film with small domains exhibits a metallic behavior and the layered WSe2 films with larger domains provides clear semiconducting behavior. Finally, an 8'' wafer scale-layered WSe2 film was demonstrated, giving a step forward in the development of 2D TMDC electronics in the industry.

Thermally Strained Band Gap Engineering of Transition-Metal Dichalcogenide Bilayers with Enhanced Light-Matter Interaction toward Excellent Photodetectors.

Integration of strain engineering of two-dimensional (2D) materials in order to enhance device performance is still a challenge. Here, we successfully demonstrated the thermally strained band gap engineering of transition-metal dichalcogenide bilayers by different thermal expansion coefficients between 2D materials and patterned sapphire structures, where MoS2 bilayers were chosen as the demonstrated materials. In particular, a blue shift in the band gap of the MoS2 bilayers can be tunable, displaying an extraordinary capability to drive electrons toward the electrode under the smaller driven bias, and the results were confirmed by simulation. A model to explain the thermal strain in the MoS2 bilayers during the synthesis was proposed, which enables us to precisely predict the band gap-shifted behaviors on patterned sapphire structures with different angles. Furthermore, photodetectors with enhancement of 286% and 897% based on the strained MoS2 on cone- and pyramid-patterned sapphire substrates were demonstrated, respectively.

Wafer Scale Phase-Engineered 1T- and 2H-MoSe2 /Mo Core-Shell 3D-Hierarchical Nanostructures toward Efficient Electrocatalytic Hydrogen Evolution Reaction.

The necessity for new sources for greener and cleaner energy production to replace the existing ones has been increasingly growing in recent years. Of those new sources, the hydrogen evolution reaction has a large potential. In this work, for the first time, MoSe2 /Mo core-shell 3D-hierarchical nanostructures are created, which are derived from the Mo 3D-hierarchical nanostructures through a low-temperature plasma-assisted selenization process with controlled shapes grown by a glancing angle deposition system.

Transfer-Free Growth of Atomically Thin Transition Metal Disulfides Using a Solution Precursor by a Laser Irradiation Process and Their Application in Low-Power Photodetectors.

Although chemical vapor deposition is the most common method to synthesize transition metal dichalcogenides (TMDs), several obstacles, such as the high annealing temperature restricting the substrates used in the process and the required transfer causing the formation of wrinkles and defects, must be resolved. Here, we present a novel method to grow patternable two-dimensional (2D) transition metal disulfides (MS2) directly underneath a protective coating layer by spin-coating a liquid chalcogen precursor onto the transition metal oxide layer, followed by a laser irradiation annealing process. Two metal sulfides, molybdenum disulfide (MoS2) and tungsten disulfide (WS2), are investigated in this work. Material characterization reveals the diffusion of sulfur into the oxide layer prior to the formation of the MS2. By controlling the sulfur diffusion, we are able to synthesize continuous MS2 layers beneath the top oxide layer, creating a protective coating layer for the newly formed TMD. Air-stable and low-power photosensing devices fabricated on the synthesized 2D WS2 without the need for a further transfer process demonstrate the potential applicability of TMDs generated via a laser irradiation process.

Direct formation of large-scale multi-layered germanene on Si substrate.

Germanene layers with lonsdaleite structure has been synthesized from a SiGe thin film for the first time using a N2 plasma-assisted process in this investigation. Multi-layered germanene can be directly observed, and the derived lattice parameters are nearly consistent with the theoretical results. Furthermore, large-scale multi-layered germanene has also been demonstrated for applications.

Plasma-Assisted Synthesis of High-Mobility Atomically Layered Violet Phosphorus.

Two-dimensional layered materials such as graphene, transition metal dichalcogenides, and black phosphorus have demonstrated outstanding properties due to electron confinement as the thickness is reduced to atomic scale. Among the phosphorus allotropes, black phosphorus, and violet phosphorus possess layer structure with the potential to be scaled down to atomically thin film. For the first time, the plasma-assisted synthesis of atomically layered violet phosphorus has been achieved. Material characterization supports the formation of violet phosphorus/InN over InP substrate where the layer structure of violet phosphorus is clearly observed. The identification of the crystal structure and lattice constant ratifies the formation of violet phosphorus indeed. The critical concept of this synthesis method is the selective reaction induced by different variations of Gibbs free energy (ΔG) of reactions. Besides, the Hall mobility of the violet phosphorus on the InP substrate greatly increases over the theoretical values of InP bulk material without much reduction in the carrier concentration, suggesting that the mobility enhancement results from the violet phosphorus layers. Furthermore, this study demonstrates a low-cost technique with high compatibility to synthesize the high-mobility atomically layered violet phosphorus and open the space for the study of the fundamental properties of this intriguing material as a new member of the fast growing family of 2D crystals.

Ultrafast and low temperature synthesis of highly crystalline and patternable few-layers tungsten diselenide by laser irradiation assisted selenization process.

Recently, a few attempts to synthesize monolayers of transition metal dichalcogenides (TMDs) using the chemical vapor deposition (CVD) process had been demonstrated. However, the development of alternative processes to synthesize TMDs is an important step because of the time-consuming, required transfer and low thermal efficiency of the CVD process. Here, we demonstrate a method to achieve few-layers WSe2 on an insulator via laser irradiation assisted selenization (LIAS) process directly, for which the amorphous WO3 film undergoes a reduction process in the presence of selenium gaseous vapors to form WSe2, utilizing laser annealing as a heating source. Detailed growth parameters such as laser power and laser irradiation time were investigated. In addition, microstructures, optical and electrical properties were investigated. Furthermore, a patternable WSe2 concept was demonstrated by patterning the WO3 film followed by the laser irradiation. By combining the patternable process, the transfer-free WSe2 back gate field effect transistor (FET) devices are realized on 300 nm-thick SiO2/P(+)Si substrate with extracted field effect mobility of ∼0.2 cm(2) V(-1) s(-1). Similarly, the reduction process by the laser irradiation can be also applied for the synthesis of other TMDs such as MoSe2 from other metal oxides such as MO3 film, suggesting that the process can be further extended to other TMDs. The method ensures one-step process to fabricate patternable TMDs, highlighting the uniqueness of the laser irradiation for the synthesis of different TMDs.