Programmable Interfacial Band Configuration in WS2/Bi2O2Se Heterojunctions.

van der Waals heterojunctions based on transition-metal dichalcogenides (TMDs) offer advanced strategies for manipulating light-emitting and light-harvesting behaviors. A crucial factor determining the light-material interaction is in the band alignment at the heterojunction interface, particularly the distinctions between type-I and type-II alignments. However, altering the band alignment from one type to another without changing the constituent materials is exceptionally difficult. Here, utilizing Bi2O2Se with a thickness-dependent band gap as a bottom layer, we present an innovative strategy for engineering interfacial band configurations in WS2/Bi2O2Se heterojunctions. In particular, we achieve tuning of the band alignment from type-I (Bi2O2Se straddling WS2) to type-II and finally to type-I (WS2 straddling Bi2O2Se) by increasing the thickness of the Bi2O2Se bottom layer from monolayer to multilayer. We verified this band architecture conversion using steady-state and transient spectroscopy as well as density functional theory calculations. Using this material combination, we further design a sophisticated band architecture incorporating both type-I (WS2 straddles Bi2O2Se, fluorescence-quenched) and type-I (Bi2SeO5 straddles WS2, fluorescence-recovered) alignments in one sample through focused laser beam (FLB). By programming the FLB trajectory, we achieve a predesigned localized fluorescence micropattern on WS2 without changing its intrinsic atomic structure. This effective band architecture design strategy represents a significant leap forward in harnessing the potential of TMD heterojunctions for multifunctional photonic applications.

Mechanomaterials and Nanomechanics: Toward Proactive Design of Material Properties and Functionalities.

While conventional mechanics of materials offers a passive understanding of the mechanical properties of materials in existing forms, a paradigm shift, referred to as mechanomaterials, is emerging to enable the proactive programming of materials' properties and functionalities by leveraging force-geometry-property relationships. One of the foundations of this new paradigm is nanomechanics, which permits functional and structural materials to be designed based on principles from the nanoscale and beyond. Although the field of mechanomaterials is still in its infancy at the present time, we discuss the current progress in three specific directions closely linked to nanomechanics and provide perspectives on these research foci by considering the potential research directions, chances for success, and existing research capabilities. We believe this new research paradigm will provide future materials solutions for infrastructure, healthcare, energy, and environment.

Upcycling fish scales through heating for steganography and Rhodamine B adsorption application.

With increasing population and limited resources, a potential route for improving sustainability is increased reuse of waste materials. By re-looking at wastes, interesting properties and multifunctionalities can be discovered in materials previously explored. Despite years of research on bio-compatible fish scales, there is limited study on the fluorescence property of this abundant waste material. Controlled denaturation of collagen and introduction of defects can serve as a means to transform the fluorescence property of these fish scale wastes while providing more adsorption sites for pollutant removal, turning multifunctional fish scales into a natural steganographic material for transmitting text and images at both the macroscopic and microscopic levels and effectively removing Rhodamine B pollutants (91 % removal) within a short contact time (10 minutes). Our work offers a glimpse into the realm of engineering defects-induced fluorescence in natural material with potential as bio-compatible fluorescence probes while encouraging multidimensional applicability to be established in otherwise overlooked waste resources.

Dynamic Tuning of Moiré Superlattice Morphology by Laser Modification.

In artificial van der Waals (vdW) layered devices, twisting the stacking angle has emerged as an effective strategy to regulate the electronic phases and optical properties of these systems. Along with the twist registry, the lattice reconstruction arising from vdW interlayer interaction has also inspired significant research interests. The control of twist angles is significantly important because the moiré periodicity determines the electron propagation length on the lattice and the interlayer electron-electron interactions. However, the moiré periodicity is hard to be modified after the device has been fabricated. In this work, we have demonstrated that the moiré periodicity can be precisely modulated with a localized laser annealing technique. This is achieved with regulating the interlayer lattice mismatch by the mismatched lattice constant, which originates from the variable density of sulfur vacancy generated during laser modification. The existence of sulfur vacancy is further verified by excitonic emission energy and lifetime in photoluminescence measurements. Furthermore, we also discover that the mismatched lattice constant has the equivalent contribution as the twist angle for determining the lattice mismatch. Theoretical modeling elaborates the moiré-wavelength-dependent energy variations at the interface and mimics the evolution of moiré morphology.

Nanopath-Beacons for Directed Silver Dendrites' Migration across Graphene Oxide Terrain.

With their special hierarchical fractal and highly symmetric formation, silver dendrites have a large surface area and plentiful active sites at edges, which have allowed them to exhibit unique properties ranging from superhydrophobic surfaces to biosensors. Yet, many suggested synthesis processes either require a long reaction time or risk contamination from sacrificial elements. Limited research in directing while enhancing the growth of these silver dendrites also hinders the application of these unique microstructures as site-selective hydrophobicity of surfaces and location-dependent SERS (surface-enhanced Raman spectroscopy). A possible solution to this is to utilize WO3 nanocubes as beacons to accelerate and conduct the growth of these silver dendrites through the electrochemical migration process. These nanocubes effortlessly altered the applied electric field distributed between the electrodes, depending on their orientations and positions. As the silver dendrites branched from the nanocubes, the dendrites themselves further concentrated the electric field to encourage the growth of more loose fractal silver dendrites. The combinatory effect successfully directs the growth of silver dendrites along the concentrated electric field paths. Both changes to the electric field and directed growth of silver dendrites are underscored using Multiphysics COMSOL simulations and time-lapse microscopy. This work provided insight into the possibility of designing microstructures to direct and accelerate the growth of silver dendrites.

Electrochemically Exfoliated Platinum Dichalcogenide Atomic Layers for High-Performance Air-Stable Infrared Photodetectors.

Platinum dichalcogenide (PtX2), an emergent group-10 transition metal dichalcogenide (TMD) has shown great potential in infrared photonic and optoelectronic applications due to its layer-dependent electronic structure with potentially suitable bandgap. However, a scalable synthesis of PtSe2 and PtTe2 atomic layers with controlled thickness still represents a major challenge in this field because of the strong interlayer interactions. Herein, we develop a facile cathodic exfoliation approach for the synthesis of solution-processable high-quality PtSe2 and PtTe2 atomic layers for high-performance infrared (IR) photodetection. As-exfoliated PtSe2 and PtTe2 bilayer exhibit an excellent photoresponsivity of 72 and 1620 mA W-1 at zero gate voltage under a 1540 nm laser illumination, respectively, approximately several orders of magnitude higher than that of the majority of IR photodetectors based on graphene, TMDs, and black phosphorus. In addition, our PtSe2 and PtTe2 bilayer device also shows a decent specific detectivity of beyond 109 Jones with remarkable air-stability (>several months), outperforming the mechanically exfoliated counterparts under the laser illumination with a similar wavelength. Moreover, a high yield of PtSe2 and PtTe2 atomic layers dispersed in solution also allows for a facile fabrication of air-stable wafer-scale IR photodetector. This work demonstrates a new route for the synthesis of solution-processable layered materials with the narrow bandgap for the infrared optoelectronic applications.

Heteromoiré Engineering on Magnetic Bloch Transport in Twisted Graphene Superlattices.

Localized electrons subject to applied magnetic fields can restart to propagate freely through the lattice in delocalized magnetic Bloch states (MBSs) when the lattice periodicity is commensurate with the magnetic length. Twisted graphene superlattices with moiré wavelength tunability enable experimental access to the unique delocalization in a controllable fashion. Here, we report the observation and characterization of high-temperature Brown-Zak (BZ) oscillations which come in two types, 1/B and B periodicity, originating from the generation of integer and fractional MBSs, in the twisted bilayer and trilayer graphene superlattices, respectively. Coexisting periodic-in-1/B oscillations assigned to different moiré wavelengths are dramatically observed in small-angle twisted bilayer graphene, which may arise from angle-disorder-induced in-plane heteromoiré superlattices. Moreover, the vertical stacking of heteromoiré supercells in double-twisted trilayer graphene results in a mega-sized superlattice. The exotic superlattice contributes to the periodic-in-B oscillation and dominates the magnetic Bloch transport.

Band Nesting Bypass in WS2 Monolayers via Förster Resonance Energy Transfer.

Two-dimensional (2D) transition-metal dichalcogenides (TMDs) have attracted intensive interest due to the direct-band-gap transition in the monolayer form, positioning them as potential next-generation materials for optoelectronic or photonic devices. However, the band-nested suppression of the recombination efficiency at higher excitation energies limits the ability to locally control and manipulate the photoluminescence of WS2 for multifunctional applications. In this work, we exploit an energy transfer method to modulate the fluorescence properties of TMDs under a larger excitation range spanning from UV to visible light. Self-assembled lanthanide (Ln)/TMD hybrids have been designed based on a low-cost and highly efficient solution-processed approach. The emission energy from Ln3+ sources can be effectively transferred to the TMD monolayers under low power exposure (0.13 mW) at room temperature, activating the characteristic monolayer fluorescence in place of Ln3+ emission signatures. The Ln/TMDs photonics can potentially tune the excitation of TMDs to provide variable yet controllable emissions. This provides a solution to the suppression of direct exciton recombination in monolayer TMDs at the band nesting resonant energy region. Our work on such Ln/TMD systems would overcome the limited excitation energy range in TMDs and extend their functionalities for optoelectronic or photonic applications.

Electrically Tailored Metachrosis in ZnO-C Nanowires.

Carbon incorporated zinc oxide (ZnO:C) nanowires (NWs) are found to be remarkable morphing NWs. We show that the physical properties of ZnO:C NWs are engineered via the passage of electric current to produce fluorescence differences and negative differential resistance as well as electroluminescence. When a ZnO:C NW is subjected to an applied voltage bias and under ultraviolet (UV) excitation, electron-hole separation due to the voltage biasing suppresses their fluorescence at low voltages. At medium voltages, the NW exhibits metastable chemical changes that translates to tunable and reversible optical alterations akin to metachrosis found in chameleons. Concurrently, the NW displays electrical alterations with negative differential resistance behaviors. At higher voltages, these NWs are permanently modified with distinct heterogeneous chemical stoichiometry, fluorescence, and electronic properties. Such heterogeneity within the NW allows for emergence of junctions capable of electroluminescence.

Fluorescence Invigoration in Carbon-Incorporated Zinc Oxide Nanowires from Passage of Field Emission Electrons.

We demonstrate that carbon incorporated Zinc Oxide (C-ZnO) nanowires (NWs) exhibit remarkable improvement in the extent and quality of fluorescence emission after they are utilized as an electron source in a field emission experiment. After the passage of field emission electrons, the intensity of the fluorescence emitted from these NWs in the visible light range exhibits a 2.5 to 8 fold enhancement. The intrinsic exciton peak of the ZnO also becomes heightened, along with the crystalline quality of the NWs showing marked improvement. This invigoration of fluorescence across the entire fluorescence spectrum is attributed to concurrent removal of oxygen and carbon atoms in C-ZnO NWs due to electro-migration of atoms and joule heating during the field emission process. Applications based on ZnO NWs emission from excitonic emissions or visible wavelength emissions or both can benefit from this straightforward method of defect engineering.

The Role of Oxygen Atoms on Excitons at the Edges of Monolayer WS2.

We clarify that the chemisorption of oxygen atoms at the edges is a key contributor to the frequently observed edge enhancement and spatial non-uniformities of photoluminescence (PL) in WS2 monolayers. Here we have investigated with momentum- and real-space nanoimaging of the chemical and electronic density inhomogeneity of WS2 flakes. Our finding from a large panoply of techniques together with density functional theory calculation confirms that the oxygen chemisorption leads to the electron accumulation at the edges. This facilitates the trion dominance of PL at the edges of WS2 flakes. Our results highlight and unravel the significance of chemisorbed oxygen at the edges in the PL emission and electronic structure of WS2, providing a viable path to enhance the performance of transition-metal-dichalcogenide-based devices.

Nanosurfer flash-mobs: electric-field-choreographed silver migration on graphene oxide.

We report for the first time the ability to direct and control the migration path of silver nanoparticles across graphene oxide (GO). With the help of a focused laser beam, we demonstrated choreographed nanoparticle assembly on GO via a directed electric-field. Silver migration and the resultant dendrite formation on GO were characterized through electrical testing coupled with fluorescence microscopy. The proposed mechanism for silver migration in GO involves the interlayer water between GO sheets serving as the electrolyte for the electrochemical process. This interlayer water facilitates the disappearance of dendrites through oxidation and dissolution into the water. Furthermore, we demonstrate that the shape of the formed Ag dendrites can be controlled by a combination of an applied electric field and patterned regions of a reduced GO film created by a focused laser beam. This paves the way for an alternative low-cost silver nanoparticle assembly method requiring only a low-powered laser and low voltage.

Progressive Micromodulation of Interlayer Coupling in Stacked WS2/WSe2 Heterobilayers Tailored by a Focused Laser Beam.

When a vertically stacked heterobilayer comprising of a WSe2 monolayer on a WS2 monolayer is first fabricated, the heterobilayer behaves like two independent monolayers because of the presence of a large interlayer separation. However, after the stacked heterobilayer is subjected to a focused laser treatment, the interlayer separation between the two monolayers becomes progressively reduced which transforms the WS2/WSe2 heterostructure from the noncoupling to the strongly coupling regime. This strong coupling induces the charge transfer between two layers and thus lowers the exciton recombination rate in the individual layer. This changes the optical properties of the heterobilayer from a fluorescence-active species into one where the fluorescence is quenched. The focused laser beam scanning method is therefore able to serve as a localized annealing tool to progressively modulate the interlayer separation and enable the micropatterning of the heterobilayer to achieve distinct regions with different degrees of fluorescence quenching. Systematic studies are carried out to gain an insight into the mechanism involved in the onset of the interlayer coupling in the material. Our method is also successfully extended to a WS2/WS2 homobilayer structure.

One-dimensional nanostructures of II-VI ternary alloys: synthesis, optical properties, and applications.

One-dimensional (1D) nanostructures of II-VI ternary alloys are of prime interest due to their compatible features of both 1D nanostructures and semiconducting alloys. These features can facilitate materials with tunable bandgaps, which are crucial to the performance of photoelectrical devices. Herein, we present a comprehensive review summarizing the recent research progress pertinent to the diverse synthesis, optical fundamentals and applications of 1D nanostructures of II-VI ternary alloys. Considering multifunctional applications, the different growth mechanisms of the rational design and synthesis techniques are highlighted. Investigations of the fundamentals of the optical and photoelectrical properties of ternary alloyed II-VI semiconductors via the corresponding characterization techniques are also particularly discussed. Furthermore, we present the versatile potential practical applications of these materials. Finally, we extend the discussion to the most recent research advances on quaternary alloys, which provides a possible prospective forecast for the sustained development of alloyed 1D nanostructures.

Tailoring sample-wide pseudo-magnetic fields on a graphene-black phosphorus heterostructure.

Spatially tailored pseudo-magnetic fields (PMFs) can give rise to pseudo-Landau levels and the valley Hall effect in graphene. At an experimental level, it is highly challenging to create the specific strain texture that can generate PMFs over large areas. Here, we report that superposing graphene on multilayer black phosphorus creates shear-strained superlattices that generate a PMF over an entire graphene-black phosphorus heterostructure with edge size of tens of micrometres. The PMF is intertwined with the spatial period of the moiré pattern, and its spatial distribution and intensity can be modified by changing the relative orientation of the two materials. We show that the emerging pseudo-Landau levels influence the transport properties of graphene-black phosphorus field-effect transistor devices with Hall bar geometry. The application of an external magnetic field allows us to enhance or reduce the effective field depending on the valley polarization with the prospect of developing a valley filter.

Laser assisted blending of Ag nanoparticles in an alumina veil: a highly fluorescent hybrid.

We report a functional hybrid made of silver nanoparticles (AgNPs) embedded in an amorphous aluminium oxide (alumina) film. This laser-initiated process allows formation of AgNPs and amorphous alumina in localized regions defined by the scanning laser beam. Due to metal enhanced fluorescence, this hybrid exhibits strong blue fluorescence emission under ultraviolet excitation. Upon irradiating with electrons at dosages of 1 to 20 mC cm-2, AgNPs become more metallic while the Al film is further oxidised. As a result, the fluorescing property is intensified. Using a hybrid irradiated with 10 mC cm-2, the electronic conductivity of the sample is improved by 11.5 times compared to that of the as-synthesized hybrid film. Excitation by UV light on the sample results in an increase in the detected current of nearly 29 times. Given that the electron beam patterned message is selectively visible only under UV or blue light irradiation, this hybrid film is thus a possible platform for steganographic transmission.

Oxygen Passivation Mediated Tunability of Trion and Excitons in MoS_{2}.

Using wide spectral range in situ spectroscopic ellipsometry with systematic ultrahigh vacuum annealing and in situ exposure to oxygen, we report the complex dielectric function of MoS_{2} isolating the environmental effects and revealing the crucial role of unpassivated and passivated sulphur vacancies. The spectral weights of the A (1.92 eV) and B (2.02 eV) exciton peaks in the dielectric function reduce significantly upon annealing, accompanied by spectral weight transfer in a broad energy range. Interestingly, the original spectral weights are recovered upon controlled oxygen exposure. This tunability of the excitonic effects is likely due to passivation and reemergence of the gap states in the band structure during oxygen adsorption and desorption, respectively, as indicated by ab initio density functional theory calculation results. This Letter unravels and emphasizes the important role of adsorbed oxygen in the optical spectra and many-body interactions of MoS_{2}.

ZnO Nano-Rod Devices for Intradermal Delivery and Immunization.

Intradermal delivery of antigens for vaccination is a very attractive approach since the skin provides a rich network of antigen presenting cells, which aid in stimulating an immune response. Numerous intradermal techniques have been developed to enhance penetration across the skin. However, these methods are invasive and/or affect the skin integrity. Hence, our group has devised zinc oxide (ZnO) nano-rods for non-destructive drug delivery. Chemical vapour deposition was used to fabricate aligned nano-rods on ZnO pre-coated silicon chips. The nano-rods' length and diameter were found to depend on the temperature, time, quality of sputtered silicon chips, etc. Vertically aligned ZnO nano-rods with lengths of 30-35 µm and diameters of 200-300 nm were selected for in vitro human skin permeation studies using Franz cells with Albumin-fluorescein isothiocyanate (FITC) absorbed on the nano-rods. Fluorescence and confocal studies on the skin samples showed FITC penetration through the skin along the channels formed by the nano-rods. Bradford protein assay on the collected fluid samples indicated a significant quantity of Albumin-FITC in the first 12 h. Low antibody titres were observed with immunisation on Balb/c mice with ovalbumin (OVA) antigen coated on the nano-rod chips. Nonetheless, due to the reduced dimensions of the nano-rods, our device offers the additional advantage of excluding the simultaneous entrance of microbial pathogens. Taken together, these results showed that ZnO nano-rods hold the potential for a safe, non-invasive, and painless intradermal drug delivery.

Microsteganography on WS2 Monolayers Tailored by Direct Laser Painting.

We present scanning focused laser beam as a multipurpose tool to engineer the physical and chemical properties of WS2 microflakes. For monolayers, the laser modification integrates oxygen into the WS2 microflake, resulting in ∼9 times enhancement in the intensity of the fluorescence emission. This modification does not cause any morphology change, allowing "micro-encryption" of information that is only observable as fluorescence under excitation. The same focused laser also facilitates on demand thinning down of WS2 multilayers into monolayers, turning them into fluorescence active components. With a scanning focused laser beam, micropatterns are readily created on WS2 multilayers through selective thinning of specific regions on the flake.