Pd Nanocluster/Monolayer MoS2 Heterojunctions for Light-Induced Room-Temperature Hydrogen Sensing.

Developing sensing approaches that can exploit visible light for the detection of low-concentration hydrogen at room temperatures has become increasingly important for the safe use of hydrogen in many applications. In this study, heterostructures composed of monolayer MoS2 and Pd nanoclusters (Pd/MoS2) acting as photo- and hydrogen-sensitizers are successfully fabricated in a facile and scalable manner. The uniform deposition of morphologically isotropic Pd nanoclusters (11.5 ± 2.2 nm) on monolayer MoS2 produces a plethora of active heterojunctions, effectively suppressing charge carrier recombination under light illumination. The dual photo- and hydrogen-sensitizing functionality of Pd/MoS2 can enable its use as an active sensing layer in optoelectronic hydrogen sensors. Gas-sensing examinations reveal that the sensing performance of Pd/MoS2 is enhanced three-fold under visible light illumination (17% for 140 ppm of H2) in comparison with dark light (5% for 140 ppm of H2). Photoactivation is also found to enable excellent sensing reversibility and reproducibility in the obtained sensor. As a proof-of-concept, the integration of Pd nanoclusters and monolayer MoS2 can open a new avenue for light-induced hydrogen gas sensing at room temperature.

Nitrogen-Plasma-Treated Continuous Monolayer MoS2 for Improving Hydrogen Evolution Reaction.

Theoretically, the edges of a MoS2 flake and S-vacancy within the lattice have nearly zero Gibbs free energy for hydrogen adsorption, which is essentially correlated to the exchange currents in hydrogen evolution reaction (HER). However, MoS2 possesses insufficient active sites (edges and S-vacancies) in pristine form. Interestingly, active sites can be effectively engineered within the continuous MoS2 sheets by treating it with plasma in a controlled manner. Here, we employed N2 plasma on a large-area continuous-monolayer MoS2 synthesized via metal-organic chemical vapor deposition to acquire maximum active sites that are indeed required for an efficient HER performance. The MoS2 samples with maximum active sites were acquired by optimizing the plasma exposure time. The newly induced edges and S-vacancies were directly verified by high-resolution transmission electron microscopy. The 20 min treated MoS2 sample showed maximum active sites and thereby maximum HER activity, onset overpotential of ∼-210 mV vs reversible hydrogen electrode (RHE), and Tafel slope of ∼89 mV/dec. Clearly, the above results show that this approach can be employed for improving the HER efficiency of large-scale MoS2-based electrocatalysts.

High Photoresponse in Conformally Grown Monolayer MoS2 on a Rugged Substrate.

Conformal growth of atomic-thick semiconductor layers on patterned substrates can boost up the performance of electronic and optoelectronic devices remarkably. However, conformal growth is a very challenging technological task, since the control of the growth processes requires utmost precision. Herein, we report on conformal growth and characterization of monolayer MoS2 on planar, microrugged, and nanorugged SiO2/Si substrates via metal-organic chemical vapor deposition. The continuous and conformal nature of monolayer MoS2 on the rugged surface was verified by high-resolution transmission electron microscopy. Strain effects were examined by photoluminescence (PL) and Raman spectroscopy. Interestingly, the photoresponsivity (∼254.5 mA/W) of as-grown MoS2 on the nanorugged substrate was 59 times larger than that of the planar sample (4.3 mA/W) under a small applied bias of 0.1 V. This value is record high when compared with all previous MoS2-based photocurrent generation under low or zero bias. Such enhancement in the photoresponsivity arises from a large active area for light-matter interaction and local strain for PL quenching, wherein the latter effect is the key factor and unique in the conformally grown monolayer on the nanorugged surface.

MoS2 monolayers on Si and SiO2 nanocone arrays: influences of 3D dielectric material refractive index on 2D MoS2 optical absorption.

Heterostructures enable the control of transport and recombination of charge carriers, which are either injected through electrodes, or created by light illumination. Instead of full 2D-material-heterostructures in device applications, using hybrid heterostructures consisting of 2D and 3D materials is an alternative approach to take advantage of the unique physical properties of 2D materials. In addition, 3D dielectric nanostructures exhibit useful optical properties such as broadband omnidirectional antireflection effects and strongly concentrated light near the surface. In this work, the optical properties of 2D MoS2 monolayers conformally coated on 3D Si-based nanocone (NC) arrays are investigated. Numerical calculations show that the absorption in MoS2 monolayers on SiO2 NC is significantly enhanced, compared with that for MoS2 monolayers on Si NC. The weak light confinement in low refractive index SiO2 NC leads to greater absorption in the MoS2 monolayers. The measured photoluminescence and Raman intensities of the MoS2 monolayers on SiO2 NC are much greater than those on Si NC, which supports the calculation results. This work demonstrates that 2D MoS2-3D Si nano-heterostructures are promising candidates for use in high-performance integrated optoelectronic device applications.

Ultrasonic-Assisted Spin-Coating: Improved Junction by Enhanced Permeation of a Coating Material within Nanostructures.

Over the last decades, the spin-coating (SC) technique has been widely used to prepare thin films of various materials in the liquid phase on arbitrary substrates. The technique simply relies on the centrifugal force to spread a coating solution radially outward over the substrate. This mechanism works fairly well for solutions with low surface tension to form thin films of reasonable junctions on smooth substrates. Here, we present a modified SC technique, namely, ultrasonic-assisted spin-coating (UASC), to form thin films of coating solution having high surface tension on rough substrates with excellent junctions. The UASC technique couples SC with an external ultrasonic wave generator to provide external perturbation to locally break down big drops of the coating material into smaller droplets via Rayleigh instability. Because of their lower mass, these tiny droplets gain low momenta and move slowly both in radial and azimuthal directions, giving them an enough time to effectively permeate within pores, thereby yielding excellent junctions. Furthermore, we also investigated the effect of junction improvement on conventional and inverted bulk heterojunction organic solar cells. Intriguingly, the organic solar cells fabricated by the UASC method showed an improved efficiency compared to typical SC owing to efficient charge transfer across the junction. These results clearly imply that UASC is a simple and powerful technique which can significantly enhance the device performance by improving the junction. Moreover, we believe that UASC can be more effective for the preparation of devices composed of multilayers of different materials having complicated nanostructures.

Photoreduction route for Cu2O/TiO2 nanotubes junction for enhanced photocatalytic activity.

Here, we synthesized copper(i) oxide and titanium dioxide nanotubes (TNTs) heterojunctions (HJs) by a photoreduction method using a low-power UV lamp without involving any additional steps, such as chemical reduction, surfactant, or protection agents. Transmission electron microscopy, X-ray diffraction, Raman scattering, X-ray photoelectron spectroscopy, diffuse reflectance spectra, and photoluminescence spectroscopy were carried out to verify the formation of a HJ between the Cu2O nanoparticles (Cu2O NPs) and TNTs. The efficiency and the rate of methylene blue photo-degradation over the Cu2O/TNTs HJ were found to be nearly double and triple compared to the isolated TNTs. The enhanced efficiency is attributed to the narrow band gap and defect states caused by the oxygen vacancies in the vicinity of HJs. Moreover, the type II band alignment of Cu2O NPs and TNTs naturally separates the photo-generated carriers and constrains the recombination process owing to the internal electric field across the Cu2O/TNTs interface.