Precise Tuning of Bilayer Ultrasmall MoS2 Featuring Inhibition of Carrier Recombination and Fast Surface Chemistry for Green H2 Evolution.

Achieving water splitting to produce green H2 , using the noble-metal-free MoS2 , has attracted huge interest from researchers. However, tuning the number of MoS2 layers precisely while obtaining small lateral sizes to surge the H2 -evolution rate is a tremendous challenge. Here, a bottom-up strategy is designed for the in situ growth of ultrasmall lateral-sized MoS2 with tunable layers on CdS nanorods (CN) by controlling the decomposition temperature and concentration of substrate seed (NH4 )2 MoS4 . Here, the bilayer MoS2 and CN coupling (2L-MoS2 /CN) exhibits the optimum photocatalytic activity. Compared to thicker MoS2 , the 2L-MoS2 has sufficient reduction capacity to drive photocatalytic H2 evolution and the ultrasmall lateral size provides more active sites. Meanwhile, the indirect bandgap, in contrast to the direct bandgap of the monolayer MoS2 , suppresses the carrier recombination transferred to 2L-MoS2 . Under the synergistic effect of both, 2L-MoS2 /CN has fast surface chemical reactions, resulting in the photocatalytic H2 -evolution rate of up to 41.86 mmol g-1 h-1 . A novel strategy is provided here for tuning the MoS2 layers to achieve efficient H2 evolution.

Characteristics of tunable aluminum-doped Ga2O3thin films and photodetectors.

Aluminum-doped Ga2O3(AGO) thin films were prepared by plasma-enhanced atomic layer deposition (PE-ALD). The growth mechanism, surface morphology, chemical composition, and optical properties of AGO films were systematically investigated. The bandgap of AGO films can be theoretically set between 4.65 and 6.8 eV. Based on typical AGO films, metal-semiconductor-metal photodetectors (PDs) were created, and their photoelectric response was examined. The preliminary results show that PE-ALD grown AGO films have high quality and tunable bandgap, and AGO PDs possess superior characterizations to undoped films. The AGO realized using PE-ALD is expected to be an important route for the development of a new generation of gallium oxide-based photodetectors into the deep-ultraviolet.

Black Phosphorus-based Photocatalysts: Synthesis, Properties, and Applications.

Photocatalysis is considered as an eco-friendly and sustainable strategy, since it uses abundant light for the advancement of the reaction, which is freely accessible and is devoid of environmental pollution. During the last decades, (nano)photocatalysts have gained broad industrial applications in terms of purification and detoxification of water as well as production of green fuels and hydrogen gas due to their special attributes. The degradation or remediation of toxic and hazardous compounds from the environment or changing them into non-toxic entities is a significant endeavor and necessary for the safety of humans, animals, and the environment. Black phosphorus (BP), a two-dimensional single-element material, has a marvelous structure, tunable bandgap, changeable morphology from bulk to nanosheet/quantum dot, and unique physicochemical properties, which makes it attractive material for photocatalytic applications, especially for sustainable development purposes. Since it can serve as a photocatalyst with or without coupling with other semiconductors, various aspects for multidimensional exploitation of BP are deliberated including their preparation via solvothermal, ball milling, calcination, and sonication methods to obtain BP from red phosphorus. The techniques for improving the photocatalytic and stability of BP-based composites are discussed along with their multifaceted applications for environmental remediation, pollution degradation, water splitting, N2 fixation, CO2 reduction, bacterial disinfection, H2 generation, and photodynamic therapy. Herein, most recent advancements pertaining to the photocatalytic applications of BP-based photocatalyst are cogitated, with a focus on their synthesis and properties as well as crucial challenges and future perspectives.

Design principles for photonic crystals based on plasmonic nanoparticle superlattices.

Photonic crystals have been widely studied due to their broad technological applications in lasers, sensors, optical telecommunications, and display devices. Typically, photonic crystals are periodic structures of touching dielectric materials with alternating high and low refractive indices, and to date, the variables of interest have focused primarily on crystal symmetry and the refractive indices of the constituent materials, primarily polymers and semiconductors. In contrast, finite difference time domain (FDTD) simulations suggest that plasmonic nanoparticle superlattices with spacer groups offer an alternative route to photonic crystals due to the controllable spacing of the nanoparticles and the high refractive index of the lattices, even far away from the plasmon frequency where losses are low. Herein, the stopband features of 13 Bravais lattices are characterized and compared, resulting in paradigm-shifting design principles for photonic crystals. Based on these design rules, a simple cubic structure with an ∼130-nm lattice parameter is predicted to have a broad photonic stopband, a property confirmed by synthesizing the structure via DNA programmable assembly and characterizing it by reflectance measurements. We show through simulation that a maximum reflectance of more than 0.99 can be achieved in these plasmonic photonic crystals by optimizing the nanoparticle composition and structural parameters.

Electrically Tunable Bandgaps in Bilayer MoS2.

Artificial semiconductors with manufactured band structures have opened up many new applications in the field of optoelectronics. The emerging two-dimensional (2D) semiconductor materials, transition metal dichalcogenides (TMDs), cover a large range of bandgaps and have shown potential in high performance device applications. Interestingly, the ultrathin body and anisotropic material properties of the layered TMDs allow a wide range modification of their band structures by electric field, which is obviously desirable for many nanoelectronic and nanophotonic applications. Here, we demonstrate a continuous bandgap tuning in bilayer MoS2 using a dual-gated field-effect transistor (FET) and photoluminescence (PL) spectroscopy. Density functional theory (DFT) is employed to calculate the field dependent band structures, attributing the widely tunable bandgap to an interlayer direct bandgap transition. This unique electric field controlled spontaneous bandgap modulation approaching the limit of semiconductor-to-metal transition can open up a new field of not yet existing applications.

Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications.

Transition metal dichalcogenides (TMDs) are a promising class of layered materials in the post-graphene era, with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior. Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties, providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs. The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable (opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts (0-100%). Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase, band alignment/structure, carrier density, and surface reactive activity, enabling novel and promising applications. This review comprehensively elaborates on atomically substitutional engineering in TMD layers, including theoretical foundations, synthetic strategies, tailored properties, and superior applications. The emerging type of ternary TMDs, Janus TMDs, is presented specifically to highlight their typical compounds, fabrication methods, and potential applications. Finally, opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.

Advances in Tunable Bandgaps of Piezoelectric Phononic Crystals.

Bandgaps of traditional phononic crystals (PCs) are determined using structural geometric parameters and material properties, and they are difficult to tune in practical applications. Piezoelectric PCs with lead zirconium titanate piezoelectric ceramics (abbreviated to piezoelectric PCs) have multi-physics coupling effects and their bandgaps can be tuned through external circuits to expand the application range of the PCs. First, the typical structures of piezoelectric PCs are summarized and analyzed. According to the structure, common tunable piezoelectric PCs can be roughly divided into three categories: PCs that only contain piezoelectric materials (single piezoelectric PCs), PCs composed of embedded piezoelectric materials in elastic materials (composite piezoelectric PCs), and PCs that are composed of an elastic base structure and attached piezoelectric patches (patch-type piezoelectric PCs). Second, the tuning methods of bandgaps for piezoelectric PCs are summarized and analyzed. Then, the calculation methods of the bandgaps of piezoelectric PCs are reviewed and analyzed. Finally, conclusions are drawn on the research status of piezoelectric PCs, shortcomings of the existing research are discussed, and future development directions are proposed.

Color-Tunable and Stable Copper Iodide Cluster Scintillators for Efficient X-Ray Imaging.

The search for color-tunable, efficient, and robust scintillators plays a vital role in the development of modern X-ray radiography. The radioluminescence tuning of copper iodide cluster scintillators in the entire visible region by bandgap engineering is herein reported. The bandgap engineering benefits from the fact that the conduction band minimum and valence band maximum of copper iodide cluster crystals are contributed by atomic orbitals from the inorganic core and organic ligand components, respectively. In addition to high scintillation performance, the as-prepared crystalline copper iodide cluster solids exhibit remarkable resistance toward both moisture and X-ray irradiation. These features allow copper iodide cluster scintillators to show particular attractiveness for low-dose X-ray radiography with a detection limit of 55 nGy s-1 , a value ≈100 times lower than a standard dosage for X-ray examinations. The results suggest that optimizing both inorganic core and organic ligand for the building blocks of metal halide cluster crystals may provide new opportunities for a new generation of high-performance scintillation materials.

Zero Dimensional-Two Dimensional Hybrid Photodetectors Using Multilayer MoS2 and Lead Halide Perovskite Quantum Dots with a Tunable Bandgap.

We report high-performance 0D-2D hybrid photodetectors integrated with tunable band gap perovskite (CsPbI3, CsXFAX-1PbI3, and FAPbI3) quantum dots and MOCVD-grown bilayer MoS2. In our hybrid structure, the lead halide PQDs can be utilized as an absorbing layer of light of specific wavelengths and transfer the photogenerated carriers to the MoS2 transport layer. With tunable wavelength lead halide PQDs, the 0D-2D hybrid photodetector shows a high responsivity up to 107 AW-1 and high specific detectivity exceeding 1013 Jones due to the difference in the built-in potential between PQDs and multilayer MoS2 layers. This work proposes the possibility of fabricating high-performance photodetectors by hybridizing PQDs of various band gaps with 2D materials.

Ferromagnetic Double Perovskite Semiconductors with Tunable Properties.

The authors successfully dope the magnetically silent double perovskite semiconductor Sr2 GaSbO6  to induce ferromagnetism and tune its bandgap, with Ga3+ partially substituted by the magnetic trivalent cation Mn3+ , in a rigid cation ordering with Sb5+ . The new ferromagnetic semiconducting Sr2 Ga1- x Mnx SbO6  double perovskite, which crystallizes in tetragonal symmetry (space group I4/m) and has tunable ferromagnetic ordering temperature and bandgap, suggests that magnetic ion doping of double perovskites is a productive avenue toward obtaining materials for application in next-generation oxide-based spintronic devices.

Bandgap-Tuned 2D Boron Nitride/Tungsten Nitride Nanocomposites for Development of High-Performance Deep Ultraviolet Selective Photodetectors.

This study presents a fast and effective method to synthesize 2D boron nitride/tungsten nitride (BN-WN) nanocomposites for tunable bandgap structures and devices. A few minutes of synthesis yielded a large quantity of high-quality 2D nanocomposites, with which a simple, low-cost deep UV photo-detector (DUV-PD) was fabricated and tested. The new device was demonstrated to have very good performance. High responsivity up to 1.17 A/W, fast response-time of lower than two milliseconds and highly stable repeatability were obtained. Furthermore, the influences of operating temperature and applied bias voltage on the properties of DUV-PD as well as its band structure shift were investigated.

Tuning Electronic Properties of the SiC-GeC Bilayer by External Electric Field: A First-Principles Study.

First-principles calculations were used to investigate the electronic properties of the SiC/GeC nanosheet (the thickness was about 8 Å). With no electric field (E-field), the SiC/GeC nanosheet was shown to have a direct bandgap of 1.90 eV. In the band structure, the valence band of the SiC/GeC nanosheet was mainly made up of C-p, while the conduction band was mainly made up of C-p, Si-p, and Ge-p, respectively. Application of the E-field to the SiC/GeC nanosheet was found to facilitate modulation of the bandgap, regularly reducing it to zero, which was linked to the direction and strength of the E-field. The major bandgap modulation was attributed to the migration of C-p, Si-p, and Ge-p orbitals around the Fermi level. Our conclusions might give some theoretical guidance for the development and application of the SiC/GeC nanosheet.

Tunable Bandgap and Optical Properties of Black Phosphorene Nanotubes.

Black phosphorus (BP), a new two-dimensional material, has been the focus of scientists' attention. BP nanotubes have potential in the field of optoelectronics due to their low-dimensional effects. In this work, the bending strain energy, electronic structure, and optical properties of BP nanotubes were investigated by using the first-principles method based on density functional theory. The results show that these properties are closely related to the rolling direction and radius of the BP nanotube. All the calculated BP nanotube properties show direct bandgaps, and the BP nanotubes with the same rolling direction express a monotone increasing trend in the value of bandgap with a decrease in radius, which is a stacking effect of the compression strain on the inner atoms and the tension strain on the outer atoms. The bending strain energy of the zigzag phosphorene nanotubes (zPNTs) is higher than that of armchair phosphorene nanotubes (aPNT) with the same radius of curvature due to the anisotropy of the BP's structure. The imaginary part of the dielectric function, the absorption range, reflectivity, and the imaginary part of the refractive index of aPNTs have a wider range than those of zPNTs, with higher values overall. As a result, tunable BP nanotubes are suitable for optoelectronic devices, such as lasers and diodes, which function in the infrared and ultra-violet regions, and for solar cells and photocatalysis.

Synthesis of Large-Size 1T' ReS2x Se2(1-x) Alloy Monolayer with Tunable Bandgap and Carrier Type.

Chemical vapor deposition growth of 1T' ReS2x Se2(1-x) alloy monolayers is reported for the first time. The composition and the corresponding bandgap of the alloy can be continuously tuned from ReSe2 (1.32 eV) to ReS2 (1.62 eV) by precisely controlling the growth conditions. Atomic-resolution scanning transmission electron microscopy reveals an interesting local atomic distribution in ReS2x Se2(1-x) alloy, where S and Se atoms are selectively occupied at different X sites in each Re-X6 octahedral unit cell with perfect matching between their atomic radius and space size of each X site. This structure is much attractive as it can induce the generation of highly desired localized electronic states in the 2D surface. The carrier type, threshold voltage, and carrier mobility of the alloy-based field effect transistors can be systematically modulated by tuning the alloy composition. Especially, for the first time the fully tunable conductivity of ReS2x Se2(1-x) alloys from n-type to bipolar and p-type is realized. Owing to the 1T' structure of ReS2x Se2(1-x) alloys, they exhibit strong anisotropic optical, electrical, and photoelectric properties. The controllable growth of monolayer ReS2x Se2(1-x) alloy with tunable bandgaps and electrical properties as well as superior anisotropic feature provides the feasibility for designing multifunctional 2D optoelectronic devices.

Unusual structural and electronic properties of porous silicene and germanene: insights from first-principles calculations.

Using first-principles calculations, we investigate the geometric structures and electronic properties of porous silicene and germanene nanosheets, which are the Si and Ge analogues of α-graphyne (referred to as silicyne and germanyne). It is found that the elemental silicyne and germanyne sheets are energetically unfavourable. However, after the C-substitution, the hybrid graphyne-like sheets (c-silicyne/c-germanyne) possess robust energetic and dynamical stabilities. Different from silicene and germanene, c-silicyne is a flat sheet, and c-germanyne is buckled with a distinct half-hilled conformation. Such asymmetric buckling structure causes the semiconducting behaviour into c-germanyne. While in c-silicyne, the semimetallic Dirac-like property is kept at the nonmagnetic state, but a spontaneous antiferromagnetism produces the massive Dirac fermions and opens a sizeable gap between Dirac cones. A tensile strain can further enhance the antiferromagnetism, which also linearly modulates the gap value without altering the direct-bandgap feature. Through strain engineering, c-silicyne can form a type-II band alignment with the MoS 2 sheet. The combined c-silicyne/MoS 2 nanostructure has a high power conversion efficiency beyond 20% for photovoltaic solar cells, enabling a fascinating utilization in the fields of solar energy and nano-devices.

Tunable Band Gap and Conductivity Type of ZnSe/Si Core-Shell Nanowire Heterostructures.

The electronic properties of zincblende ZnSe/Si core-shell nanowires (NWs) with a diameter of 1.1-2.8 nm are calculated by means of the first principle calculation. Band gaps of both ZnSe-core/Si-shell and Si-core/ZnSe-shell NWs are much smaller than those of pure ZnSe or Si NWs. Band alignment analysis reveals that the small band gaps of ZnSe/Si core-shell NWs are caused by the interface state. Fixing the ZnSe core size and enlarging the Si shell would turn the NWs from intrinsic to p-type, then to metallic. However, Fixing the Si core and enlarging the ZnSe shell would not change the band gap significantly. The partial charge distribution diagram shows that the conduction band maximum (CBM) is confined in Si, while the valence band maximum (VBM) is mainly distributed around the interface. Our findings also show that the band gap and conductivity type of ZnSe/Si core-shell NWs can be tuned by the concentration and diameter of the core-shell material, respectively.

Fringe structures and tunable bandgap width of 2D boron nitride nanosheets.

We report studies of the surface fringe structures and tunable bandgap width of atomic-thin boron nitride nanosheets (BNNSs). BNNSs are synthesized by using digitally controlled pulse deposition techniques. The nanoscale morphologies of BNNSs are characterized by using scanning electron microscope (SEM), and transmission electron microscopy (TEM). In general, the BNNSs appear microscopically flat in the case of low temperature synthesis, whereas at high temperature conditions, it yields various curved structures. Experimental data reveal the evolutions of fringe structures. Functionalization of the BNNSs is completed with hydrogen plasma beam source in order to efficiently control bandgap width. The characterizations are based on Raman scattering spectroscopy, X-ray diffraction (XRD), and FTIR transmittance spectra. Red shifts of spectral lines are clearly visible after the functionalization, indicating the bandgap width of the BNNSs has been changed. However, simple treatments with hydrogen gas do not affect the bandgap width of the BNNSs.