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.

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.

Light-Matter Interactions in Phosphorene.

Since the beginning of 2014, phosphorene, a monolayer or few-layer of black phosphorus, has been rediscovered as a two-dimensional (2D) thin film, revealing a plethora of properties different from the bulk material studied so far. Similar to graphene and transition metal dichalcogenides (TMDs), phosphorene is also a layered material that can be exfoliated to yield individual layers. It is one of the few monoelemental 2D crystals and the only one, besides graphene, known to be stable in monolayer, few layer, and bulk form. Recently the intensified research in phosphorene is motivated not only by the study of its fundamental physical properties in the 2D regime, such as tunable bandgap and anisotropic behavior, but also by the high carrier mobility and good on/off ratio of phosphorene-based device prototypes, making it a potential alternative for next generation nanooptoelectronics and nanophotonics applications in the "post-graphene age" The electronic bandgap of phosphorene changes from 0.3 eV in the bulk to 2.1 eV in monolayer. Thus, phosphorene exhibits strong light-matter interactions in the visible and infrared (IR) frequencies. In this Account, we present the progress on understanding the various interactions between light and phosphorene, giving insight into the mechanism of these interactions and the respective applications. We begin by discussing the fundamental optical properties of phosphorene, using theoretical calculations to depict the layer-dependent electronic band structures and anisotropic optical properties. Many-body effects in phosphorene, including excitons and trions and their binding energies and dynamics are reviewed as observed in experiments. For phosphorene, the fast degradation in ambient condition, caused by photoinduced oxidation, is considered as a longstanding challenge. In contrast, oxidation can be used to engineer the band structure of phosphorene and, in parallel, its optical properties. Based on the strong light-matter interactions, we introduce a controllable method to directly oxidize phosphorene by laser techniques. With the oxidization induced by laser scanning, localized bandgap engineering can be achieved and microphotonics are demonstrated on the oxidized phosphorene. Finally, we will present a brief discussion on the realization of phosphorene-based building blocks of optoelectronic devices. Naturally, the strong light-matter interactions in phosphorene could enable efficient photoelectric conversion in optoelectronic devices. We will describe high performance photodetectors based on phosphorene, and the working mechanism of those devices will be introduced. The photovoltaic effect could also be exhibited in phosphorene. This indicates the pervasive potential of phosphorene in nanooptoelectronics.

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}.

Interactions between lasers and two-dimensional transition metal dichalcogenides.

The recent increasing research interest in two-dimensional (2D) layered materials has led to an explosion of in the discovery of novel physical and chemical phenomena in these materials. Among the 2D family, group-VI transition metal dichalcogenides (TMDs), such as represented by MoS2 and WSe2, are remarkable semiconductors with sizable energy band gaps, which make the TMDs promising building blocks for new generation optoelectronics. On the other hand, the specificity and tunability of the band gaps can generate particularly strong light-matter interactions between TMD crystals and specific photons, which can trigger complex and interesting phenomena such as photo-scattering, photo-excitation, photo-destruction, photo-physical modification, photochemical reaction and photo-oxidation. Herein, we provide an overview of the phenomena explained by various interactions between lasers and the 2D TMDs. Characterizations of the optical fundamentals of the TMDs via laser spectroscopies are reviewed. Subsequently, photoelectric conversion devices enabled by laser excitation and the functionality extension and performance improvement of the TMDs materials via laser modification are comprehensively summarized. Finally, we conclude the review by discussing the prospects for further development in this research area.

Fluorescence Concentric Triangles: A Case of Chemical Heterogeneity in WS2 Atomic Monolayer.

We report a novel optical property in WS2 monolayer. The monolayer naturally exhibits beautiful in-plane periodical and lateral homojunctions by way of alternate dark and bright band in the fluorescence images of these monolayers. The interface between different fluorescence species within the sample is distinct and sharp. This gives rise to intriguing concentric triangular fluorescence patterns in the monolayer. The novel optical property of this special WS2 monolayer is facilitated by chemical heterogeneity. The photoluminescence of the bright band is dominated by emissions from trion and biexciton while the emission from defect-bound exciton dominates the photoluminescence at the dark band. The discovery of such concentric fluorescence patterns represents a potentially new form of optoelectronic or photonic functionality.

Atomic healing of defects in transition metal dichalcogenides.

As-grown transition metal dichalcogenides are usually chalcogen deficient and therefore contain a high density of chalcogen vacancies, deep electron traps which can act as charged scattering centers, reducing the electron mobility. However, we show that chalcogen vacancies can be effectively passivated by oxygen, healing the electronic structure of the material. We proposed that this can be achieved by means of surface laser modification and demonstrate the efficiency of this processing technique, which can enhance the conductivity of monolayer WSe2 by ∼400 times and its photoconductivity by ∼150 times.

Hybrid Bilayer WSe2 -CH3 NH3 PbI3 Organolead Halide Perovskite as a High-Performance Photodetector.

A high-performance 2D photodetector based on a bilayer structure comprising a WSe2 monolayer and CH3 NH3 PbI3 organolead halide perovskite is reported. High performance is realized by modification of the WSe2 monolayer with laser healing and perovskite functionalization. After modification, the output of the device was three orders of magnitude better than the pristine device; the performance is superior to that of most of the 2D photodetectors based on transition-metal-dichalcogenides (TMDs). This result indicates that combinatory TMDs-halide perovskite hybrids can be promising building blocks in optoelectronics.

Microlandscaping of Au nanoparticles on few-layer MoS2 films for chemical sensing.

Surface modification or decoration of ultrathin MoS2 films with chemical moieties is appealing since nanointerfacing can functionalize MoS2 films with bonus potentials. In this work, a facile and effective method for microlandscaping of Au nanoparticles (NPs) on few-layer MoS2 films is developed. This approach first employs a focused laser beam to premodify the MoS2 films to achieve active surface domains with unbound sulfur. When the activated surface is subsequently immersed in AuCl3 solution, Au NPs are found to preferentially decorate onto the modified regions. As a result, Au NPs can be selectively and locally anchored onto designated regions on the MoS2 surface. With a scanning laser beam, microlandscapes comprising of Au NPs decorated on laser-defined micropatterns are constructed. By varying the laser power, reaction time and thickness of the MoS2 films, the size and density of the NPs can be controlled. The resulting hybrid materials are demonstrated as efficient Raman active surfaces for the detection of aromatic molecules with high sensitivity.

Tuning the electronic properties of ZnO nanowire field effect transistors via surface functionalization.

Using in situ field effect transistor (FET) characterization combined with the molecular beam epitaxy technique, we demonstrate a significant depletion of electron charge carriers in single zinc oxide (ZnO) nanowire through the surface modification with molybdenum trioxide (MoO3) and 1, 4, 5, 8, 9, 11-hexaazatriphenylene hexacarbonitrile (HATCN) layers. The electron mobility of ZnO nanowire was found to sharply decrease after the surface modification with MoO3; in contrast, the electron mobility significantly increased after functionalization with HATCN layers. Such depletion of n-type conduction originates from the interfacial charge transfer, corroborated by in situ photoelectron spectroscopy studies. The air exposure effect on MoO(3-) and HATCN-coated ZnO nanowire devices was also investigated.

Composition-dependent electron transport in CdS(x)Se(1-x) nanobelts: a THz spectroscopy study.

We present a study on the composition-dependent electron transport in ternary CdS(x)Se(1-x) nanobelts at equilibrium and nonequilibrium conditions via THz spectroscopy. The measured spectra are analyzed using a Drude-Smith model combined with a harmonic oscillator. The physical origin of parameters in the Drude-Smith model is studied in detail. Under equilibrium conditions, the surface depletion region is the dominant factor to free-carrier backscattering. However, under nonequilibrium conditions, the influence of the surface depletion region is masked by the high bulk concentration and the free carriers are mainly localized by composition disorder. The contributions from different mechanisms to the carrier mobility are also explored. In equilibrium, alloy scattering is the most vital scattering mechanism for nanobelts with x=0.25→0.9 since composition disorder is significant in this range. On the other hand, the effect of electron-phonon interaction increases under photoexcitation.

Ultrathin hexagonal hybrid nanosheets synthesized by graphene oxide-assisted exfoliation of ß-Co(OH)2 mesocrystals.

In the present study, we report the synthesis of a high-quality, single-crystal hexagonal ß-Co(OH)2 nanosheet, exhibiting a thickness down to ten atomic layers and an aspect ratio exceeding 900, by using graphene oxide (GO) as an exfoliant of ß-Co(OH)2 nanoflowers. Unlike conventional approaches using ionic precursors in which morphological control is realized by structure-directing molecules, the ß-Co(OH)2 flower-like superstructures were first grown by a nanoparticle-mediated crystallization process, which results in large 3D superstructure consisting of ultrathin nanosheets interspaced by polydimethoxyaniline (PDMA). Thereafter, ß-Co(OH)2 nanoflowers were chemically exfoliated by surface-active GO under hydrothermal conditions into unilamellar single-crystal nanosheets. In this reaction, GO acts as a two-dimensional (2D) amphiphile to facilitate the exfoliation process through tailored interactions between organic and inorganic molecules. Meanwhile, the on-site conjugation of GO and Co(OH)2 promotes the thermodynamic stability of freestanding ultrathin nanosheets and restrains further growth through Oswald ripening. The unique 2D structure combined with functionalities of the hybrid ultrathin Co(OH)2 nanosheets on rGO resulted in a remarkably enhanced lithium-ion storage performance as anode materials, maintaining a reversible capacity of 860 mA h g(-1) for as many as 30 cycles. Since mesocrystals are ubiquitous and rich in morphological diversity, the strategy of the GO-assisted exfoliation of mesocrystals developed here provides an opportunity for the synthesis of new functional nanostructures that could bear importance in clean renewable energy, catalysis, photoelectronics, and photonics.

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.

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.

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.

Reduced graphene oxide conjugated Cu2O nanowire mesocrystals for high-performance NO2 gas sensor.

Reduced graphene oxide (rGO)-conjugated Cu(2)O nanowire mesocrystals were formed by nonclassical crystallization in the presence of GO and o-anisidine under hydrothermal conditions. The resultant mesocrystals are comprised of highly anisotropic nanowires as building blocks and possess a distinct octahedral morphology with eight {111} equivalent crystal faces. The mechanisms underlying the sequential formation of the mesocrystals are as follows: first, GO-promoted agglomeration of amorphous spherical Cu(2)O nanoparticles at the initial stage, leading to the transition of growth mechanism from conventional ion-by-ion growth to particle-mediated crystallization; second, the evolution of the amorphous microspheres into hierarchical structure, and finally to nanowire mesocrystals through mesoscale transformation, where Ostwald ripening is responsible for the growth of the nanowire building blocks; third, large-scale self-organization of the mesocrystals and the reduction of GO (at high GO concentration) occur simultaneously, resulting in an integrated hybrid architecture where porous three-dimensional (3D) framework structures interspersed among two-dimensional (2D) rGO sheets. Interestingly, "super-mesocrystals" formed by 3D oriented attachment of mesocrystals are also formed judging from the voided Sierpinski polyhedrons observed. Furthermore, the interior nanowire architecture of these mesocrystals can be kinetically controlled by careful variation of growth conditions. Owing to high specific surface area and improved conductivity, the rGO-Cu(2)O mesocrystals achieved a higher sensitivity toward NO(2) at room temperature, surpassing the performance of standalone systems of Cu(2)O nanowires networks and rGO sheets. The unique characteristics of rGO-Cu(2)O mesocrystal point to its promising applications in ultrasensitive environmental sensors.

Diameter-dependent thermal transport in individual ZnO nanowires and its correlation with surface coating and defects.

A systematic study of the thermal transport properties of individual single-crystal zinc oxide (ZnO) nanowires (NWs) with diameters in the range of ∼50-210 nm is presented. The thermal conductivity of the NWs is found to be dramatically reduced by at least an order of magnitude compared to bulk values, due to enhanced phonon-boundary scattering with a reduction in sample size. While the conventional phonon transport model can qualitatively explain the temperature dependence, it fails to account for the diameter dependence. An empirical relationship for assessing diameter-dependent thermal properties is observed, which shows an approximately linear dependence of the thermal conductivity on the cross-sectional area of the NWs in the measured diameter range. Furthermore, it is found that an amorphous-carbon layer coating on the NWs does not perturb the thermal properties of the NW cores, whereas 30 keV Ga(+) ion irradiation at low dose (∼4 × 10(14) cm(-2)) leads to a remarkable reduction of the thermal conductivity of the ZnO NWs.

Plasmon-enhanced photocatalytic properties of Cu2O nanowire-Au nanoparticle assemblies.

Cu(2)O-Au nanocomposites (NCs) with tunable coverage of Au were prepared by a facile method of mixing gold nanoparticles (Au NPs) with copper(I) oxide nanowires (Cu(2)O NWs) in various ratios. These Cu(2)O-Au NCs display tunable optical properties, and their photocatalytic properties were dependent on the coverage density of Au NPs. The photocatalytic activity of Cu(2)O-Au NCs was examined by photodegradation of methylene blue. The presence of Au NPs enhanced the photodegradation efficiency of Cu(2)O NCs. The photocatalytic efficiency of Cu(2)O-Au NCs initially increased with the increasing coverage density of Au NPs and then decreased as the surface of Cu(2)O became densely covered by Au NPs. The enhanced photocatalytic efficiency was ascribed to enhanced light absorption (by the surface plasmon resonance) and the electron sink effect of the Au NPs.

Localized photo-induced voltage with controlled polarity in single K enriched MoO3 nanobundle.

The photo-induced voltage in an individual K enriched MoO(3) nanobundle was studied with localized focused laser beam irradiation. Without an external bias voltage, a significant photo-induced voltage (36.5 mV) was produced in a single nanobundle under low laser power (2.2 mW). Remarkably, the amplitude and polarity of the voltage could be controlled by the location of the focused laser spot. Unlike the common photo-response that comes from metal-semiconductor junction or PN junction in hybrid nanomaterial, the observed photo-induced effect is from the nanobundle itself, attributed to the small band gap of the material.

Enhanced electron field emission properties of high aspect ratio silicon nanowire-zinc oxide core-shell arrays.

The enhanced electron field emission (EFE) properties of high aspect ratio, vertically aligned SiNW-ZnO core-shell arrays are presented. These core-shell arrays are prepared by a thin, controlled, highly crystalline and conformal coating of zinc oxide as shell using the plasma assisted-atomic layer deposition (PA-ALD) route on vertically aligned silicon nanowire arrays core. The core-shell nanostuctures are confirmed by HRTEM imaging along with the individual elemental mapping demonstrating the conformal deposition of 10 nm ZnO on the SiNWs. EFE properties of va-SiNW-ZnO core-shell arrays showed a high emission current density of 51 µA cm(-2) and a low turn on field of 7.6 V µm(-1) (defined at a current density of 1 µA cm(-2)) compared to the 3.2 µA cm(-2) emission current density and 9.1 V µm(-1) turn on field for SiNWs. The field enhancement factor (ß) of 4227 for the devices demonstrates that these core-shell nanowire arrays are excellent field-emitters. Such an enhancement in the field emission originates from the details of the band structure of this peculiar material combination resulting in good electron transport from SiNW to ZnO as evident from the band diagram of the core-shell material. This is further supported by the conducting AFM studies where lowering in threshold voltage by 1 eV confirms the role of ZnO coating in the enhancement of the emission characteristics.