Actively tunable and switchable terahertz metamaterials with multi-band perfect absorption and polarization conversion.

In this paper, we theoretically present and numerically demonstrate an actively tunable and switchable multi-functional metamaterial based on vanadium dioxide (VO2) and graphene in the terahertz region. When VO2 is in the metallic phase, the proposed metamaterial serves as a multi-band perfect absorber, which exhibits the characteristics of insensitive polarization and robust tolerance for variations of the incidence angle. When VO2 is in the insulator phase, the proposed metamaterial acts as a polarization converter, which can simultaneously achieve perfect linear-to-linear and linear-to-circular polarization conversions. The simulation results show the cross-polarization conversion rate can reach ∼100% at the frequency region from 6.09 to 6.43 THz as well as 8.15 THz. Moreover, the ellipticity of linear-to-circular polarization conversion reaches ±1 at frequencies of 5.75 and 8.34 THz, respectively, which means the linear polarization waves can be completely converted into circular polarization waves. The proposed metamaterial provides new insight for the design of optoelectronic devices with multi-functionality in the terahertz region.

Switchable asymmetric transmission with broadband polarization conversion in vanadium dioxide-assisted terahertz metamaterials.

In this paper, we theoretically present a vanadium dioxide (VO2)-integrated metamaterial, which can achieve switchable single- and double-band asymmetric transmission (AT) in terahertz regions. When VO2 acts as a metal, the presented metamaterial device exhibits a single-band AT effect. In contrast, when VO2 transitions from the metal to the insulating state, a dual-band AT effect can be realized for the presented metamaterials. Also, it is demonstrated that there is a broadband near-perfect orthogonal polarization conversion associated with the AT effect. And the operating mechanisms are elucidated by using the Fabry-Pérot-like cavity model and the electromagnetic field distributions. Moreover, the presented nanostructure exhibits a robust tolerance for the incidence angle. Our designed metamaterial may have potential applications for switchable multi-functional devices in terahertz regimes.

Construction of Cu7 S4 @CuCo2 O4 Yolk-Shell Microspheres Composite and Elucidation of Its Enhanced Photocatalytic Activity, Mechanism, and Pathway for Carbamazepine Degradation.

Water pollution caused by the massive use of medicines has caused significant environmental problems. This work first reports the synthesis and characterization of the Cu7 S4 /CuCo2 O4 (CS/CCO) yolk-shell microspheres via hydrothermal and annealing methods, and then investigates their photocatalytic performance in removing organic water pollutants. The 10-CS/CCO composite with yolk-shell microspheres exhibits the highest photodegradation rate of carbamazepine (CBZ), reaching 96.3% within 2 h. The 10-CS/CCO also demonstrates more than two times higher photodegradation rates than the pure (Cu7 S4 ) CS and (CuCo2 O4 ) CCO. This outstanding photocatalytic performance can be attributed to the unique yolk-shell structure and the Z-scheme charge transfer pathway, reducing multiple reflections of the acting light. These factors enhance the light absorption efficiency and efficiently transfer photoexcited charge carriers. In-depth, photocatalytic degradation pathways of CBZ are systematically evaluated via the identification of degradation intermediates with Fukui index calculation. The insights gained from this work can serve as a guideline for developing low-cost and efficient Z-scheme photocatalyst composites with the yolk-shell structure.

Mechanistic insight into the charge carrier separation and molecular oxygen activation of manganese doping BiOBr hollow microspheres.

High-efficiency separation of photogenerated charges and molecular oxygen activation is very important for photocatalytic removal of organic pollutants. However, the current understanding of the effect mechanism of metal substitution for the separation of photo-generated charges and molecular oxygen activation is still poor. Herein, efficient manganese (Mn)-doped BiOBr hollow microspheres synthesis, systematic characterizations, and theoretical calculation discovered that Mn-doping could not only induce produce oxygen vacancies (OVs), but also can act as active sites for catalytic reactions. The induced production of OVs and Mn2+/Mn3+ by Mn optimal doping introduced into BiOBr can synergistic promote the separation of photogenerated charges and molecular oxygen activation leads to significantly enhances degradation of crystal violet (CV). Upon analysis, Mn-doping introducing unsaturated d-orbital with bridging O2- formation π-donation accelerated the separation of photo-generated charges. Meanwhile, the larger overlap of Mn-3d orbitals with O2-2p orbitals forms a π-donation bond with charge transfer from metal to O2 leading to the oxygen-oxygen (OO) bond length and molecular oxygen activation. Finally, we proposed a possible mechanism to explain the highly efficient photocatalytic degradation performance of the acquired photocatalysts. This study provides not only a novel strategy for the rational design of highly active photocatalysts, but also in-depth insights into the separation of photo-generated charges and molecular oxygen activation.

Novel scheme towards interfacial charge transfer between ZnIn2S4 and BiOBr for efficient photocatalytic removal of organics and chromium (VI) from water.

Construction of Z-scheme heterostructure is an effective strategy to enhance the charge carriers' separation. However, successfully achieving this on the defect heterojunction to improve the photocatalytic activity remains challenging. This work successfully obtained sulfur vacancy in the ZnIn2S4/BiOBr (SZIS/BOB) heterojunction composites with S-O covalent bonding using a hydrothermal method. As a result, they exhibited superior photocatalytic and stability performance. The optimized SZIS/BOB-10 exhibited excellent rhodamine B degradation (95.2%) and chromium (VI) reduction (97.8%) within 100 min under visible light. The enhanced composites with S-vacancies, S-O bond, and internal electric field induced the Z-scheme charge transfer mechanism. We had verified this mechanism based on the surface photovoltage spectra, electron spin response spectra, and density functional theory calculations. This work not only provides valuable insights into designing photocatalysts with a direct Z scheme heterostructure but also delineates a promising strategy for developing efficient photocatalysts to degrade organic pollutants.

Electron beam-induced athermal nanowelding of crossing SiO x amorphous nanowires.

Nanowelding of two crossing amorphous SiO x nanowires induced by uniform electron beam irradiation at room temperature was demonstrated in an in situ transmission electron microscope. It was observed that, under the electron beam irradiation, the amorphous nanowires became unstable driven by nanocurvature non-uniformly distributed over the nanowire surface centered around the crossing site of the nanowires. Such an instability of the nanowires could give rise to an athermal fast and massive migration of atoms nearby the surface centered around the crossing site, and thus the two crossing nanowires become gradually welded. The existing knock-on mechanism and molecular dynamics simulations seem inadequate to explain the observed athermal migration of the surface atoms and the resulting structural change at the nanoscale. To elucidate the observed phenomena of nanowelding, a mechanism of athermal atomic diffusion driven by the effects of the nanocurvature as well as the athermal activation of the electron beam was proposed and simulated. The simulation revealed the detailed process of the nanowelding and corresponding effects of the nanocurvature and athermal activation of the electron beam. In doing so, the nanowelding parameters became predictable, controllable, and tunable to a desired welding effect.

Triple-Band Anisotropic Perfect Absorbers Based on α-Phase MoO3 Metamaterials in Visible Frequencies.

Anisotropic materials provide a new platform for building diverse polarization-dependent optical devices. Two-dimensional α-phase molybdenum trioxides (α-MoO3), as newly emerging natural van der Waals materials, have attracted significant attention due to their unique anisotropy. In this work, we theoretically propose an anisotropic perfect metamaterial absorber in visible frequencies, the unit cell of which consists of a multi-layered α-MoO3 nanoribbon/dielectric structure stacked on a silver substrate. Additionally, the number of perfect absorption bands is closely related to the α-MoO3 nanoribbon/dielectric layers. When the proposed absorber is composed of three α-MoO3 nanoribbon/dielectric layers, electromagnetic simulations show that triple-band perfect absorption can be achieved for polarization along [100], and [001] in the direction of, α-MoO3, respectively. Moreover, the calculation results obtained by the finite-difference time-domain (FDTD) method are consistent with the effective impedance of the designed absorber. The physical mechanism of multi-band perfect absorption can be attributed to resonant grating modes and the interference effect of Fabry-Pérot cavity modes. In addition, the absorption spectra of the proposed structure, as a function of wavelength and the related geometrical parameters, have been calculated and analyzed in detail. Our proposed absorber may have potential applications in spectral imaging, photo-detectors, sensors, etc.

Controllable fabrication and self-assembly of Cu nanostructures: the role of Cu2+ complexes.

The controllable fabrication of low dimensional nanostructures and the assembly of nanostructures into hierarchical higher order structures at the atomic or molecular level have been two hot-spots of current nano research. In this work, the fabrication and self-assembly of Cu nanostructures were carried out by reducing Cu2+ complexes in a mixed aqueous solution of NaOH and hydrazine hydrate at a water bath temperature of 60 °C. The reduction products were characterized using a metalloscope, a scanning electron microscope, a transmission electron microscope and a powder X-ray diffractometer. It was found that the fabrication and self-assembly of Cu nanostructures can be easily realized by controlling the types of Cu2+ complexes such as [Cu(OH)4]2-, [Cu(EDA)2]2+ and [Cu(EDA)(OH)2]. The authors further analyzed the important roles of Cu2+ complexes in the fabrication and self-assembly of Cu nanostructures. It was concluded that the Cu2+ complexes in the aqueous solution would spontaneously arrange into a certain soft template according to the principle of "like dissolves like" and the action of electrostatic forces of positive and negative charges. The as-formed templates determine the fabrication and self-assembly routes and the final products of the Cu nanostructures. Therefore, it provides a controllable and universal method for both fabrication and self-assembly of Cu nanostructures, which may have potential applications in the fields of electronic and optoelectronic nanodevices in the future.

Nanoinstabilities of Cu2O porous nanostructured films as driven by nanocurvature effect and thermal activation effect.

In this work, the instabilities at the nanoscale (i.e. nanoinstabilities) of triangular pyramids-like Cu2O porous nanostructured films (PNFs) are studied by heating treatments under different atmosphere and temperature. It is found that the nanoscale building triangular pyramids turn round preferentially at the sharp angles and/or coalesce with their contacting ones by directional diffusion and plastic flow of atoms, which are driven by the nonuniformly-distributed surface nanocurvature. As a result, the triangular pyramids become quasi-sphere shape and the PNF evolves into a big, dense particles film. It is also observed that the heating or thermal activation effect efficiently promotes the reduction or oxidation of Cu2O pyramids and the crystallization or growth of the as-achieved Cu or CuO grains. The above physical and chemical instabilities or changes at the nanoscale of Cu2O PNFs can be well accounted for by the combined mechanism of nanocurvature effect and thermal activation effect. The nanocurvature effect can lower the energy barrier for the atom diffusion or plastic flow and lower the activation energy for the chemical reactions, while the thermal activation effect can supply the required kinetic energy or activation energy and make the atomic transportations and reactions kinetically possible. The findings reveal the evolution laws of morphology, crystal structure and composition of triangular pyramids-like Cu2O PNF during heating treatments, which can further be extended to other types of Cu2O PNFs. Also, the findings have important implications for the nanoinstabilities of Cu2O PNFs-based devices, especially those working at a high temperature.

Cu2O porous nanostructured films fabricated by positive bias sputtering deposition.

In this work, the authors fabricated Cu2O porous nanostructured films (PNFs) on glass slide substrates by the newly developed positive bias deposition approach in a balanced magnetron sputtering (MS) system. It was found that the surface morphology, crystal structure and optical property of the as-deposited products were greatly dependent on the applied positive substrate bias. In particular, when the substrate was biased at +50 and +150 V, both of the as-prepared Cu2O PNFs exhibited a unique triangular pyramids-like structure with obvious edges and corners and little gluing, a preferred orientation of (111) and a blue shift of energy band gap at 2.35 eV. Quantitative calculation results indicated that the traditional bombardment effects of electrons and sputtering argon ions were both negligible during the bias deposition in the balanced MS system. Instead, a new model of tip charging effect was further proposed to account for the controllable formation of PNFs by the balanced bias sputtering deposition.

Fabrication and Photocatalytic Property of Novel SrTiO3/Bi5O7I Nanocomposites.

The novel SrTiO3/Bi5O7I nanocomposites were successfully fabricated by a thermal decomposition approach. The as-prepared samples were characterized by XRD, XPS, SEM, EDS, FTIR, DRS and PL spectra. The results show that the SrTiO3/Bi5O7I nanocomposites are composed of perovskite SrTiO3 nanoparticles and tetragonal Bi5O7I nanorods. The SrTiO3/Bi5O7I nanocomposites exhibit an excellent photocatalytic performance for the degradation of RhB solution under simulated solar light irradiation, which is superior to that of pristine Bi5O7I and SrTiO3. In particular, the 30 wt% SrTiO3/Bi5O7I nanocomposite is found as the optimal composites, over which the dye degradation reaches 89.6% for 150 min of photocatalysis. The photocatalytic degradation rate of the 30 wt% SrTiO3/Bi5O7I nanocomposite is found to be 3.97 times and 12.5 times higher than that of bare Bi5O7I and SrTiO3, respectively. The reactive species trapping experiments suggest that [Formula: see text] and holes are the main active species responsible for the RhB degradation. In addition, the PL spectra elucidate the effective separation of photoinduced electron-hole pairs. Further, the possible photocatalytic mechanism of the SrTiO3/Bi5O7I nanocomposites is also elucidated based on the experimental evidences.

In situ TEM observation of preferential amorphization in single crystal Si nanowire.

The nanoinstability of a single crystal Si nanowire under electron beam irradiation was in situ investigated at room temperature by the transmission electron microscopy technique. It was observed that the Si nanowire amorphized preferentially from the surface towards the center, with the increasing of the electron dose. In contrast, in the center of the Si nanowire the amorphization seemed much more difficult, being accompanied by the rotation of crystal grains and the compression of d-spacing. Such a preferential amorphization, which is athermally induced by the electron beam irradiation, can be well accounted for by our proposed concepts of the nanocurvature effect and the energetic beam-induced athermal activation effect, while the classical knock-on mechanism and the electron beam heating effect seem inadequate to explain these processes. Furthermore, the findings revealed the difference of amorphization between a Si nanowire and a Si film under electron beam irradiation. Also, the findings have important implications for the nanoinstability and nanoprocessing of future Si nanowire-based devices.

Coalescence between Au nanoparticles as induced by nanocurvature effect and electron beam athermal activation effect.

The coalescence of two single-crystalline Au nanoparticles on surface of amorphous SiOx nanowire, as induced by electron beam irradiation, was in situ studied at room temperature in a transmission electron microscope. It was observed that along with shrinkage of the SiOx nanowire during irradiation, adjacent Au nanoparticles moved around and migrated close to each other. Once the two nanoparticles contacted with each other, a fast, massive atom transportation took place along their contact surface, where a neck region was created. With a further irradiation, the two nanoparticles rotated, aligning their crystal orientations, and gradually coalesced into a larger single-crystalline nanoparticle. The above coalescence process demonstrated an intriguing surface nanowetting ability and nanograin boundary dislocation climb and slip of Au NPs at room temperature as driven by the non-uniformly distributed nanocurvature over the surface of the two contacting nanoparticles as well as the beam-induced instability and soft mode of atomic vibration, which have been underestimated or neglected in the existing theoretical descriptions or simulations.

Fabrication and photocatalytic property of magnetic SrTiO3/NiFe2O4 heterojunction nanocomposites.

Novel multifunctional SrTiO3/NiFe2O4 nanocomposites were successfully fabricated via a two-step route. The as-prepared samples were characterized by using X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), field-emission transmission electron microscopy (TEM), UV-visible diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy and vibrating sample magnetometry (VSM). The results indicate that the SrTiO3/NiFe2O4 heterostructures are composed of SrTiO3 spheroidal nanoparticles adhered to NiFe2O4 polyhedra. The heterojunction established in the composite material accelerates the process of electron-hole pair separation and boosts the photo-Fenton reaction. Among the samples, 15 wt% SrTiO3/NiFe2O4 nanocomposites exhibit a powerful light response and excellent room temperature ferromagnetism. Subsequently, the photocatalytic degradation of RhB over the as-prepared samples was investigated and optimized, revealing that the 15 wt% SrTiO3/NiFe2O4 nanocomposites exhibit the best photocatalytic activity and stability under simulated solar light irradiation. Furthermore, according to experimental results, the possible mechanism of improved photocatalytic activity was also proposed.

Fabrication of novel AgBr/Bi24O31Br10 composites with excellent photocatalytic performance.

Novel porous AgBr/Bi24O31Br10 (AB/BOB) heterojunction composites were prepared by a hydrothermal calcination-ion exchange route and their physico-chemical properties were characterized by XRD, XPS, SEM, EDX, UV-vis DRS, BET and electrochemical measurements. The photocatalytic activity of the composites consisting of different AB/BOB mass ratios was evaluated by degradation of methylene blue (MB) under visible light irradiation. Compared with pure AB and BOB, the porous 20% AB/BOB composite exhibits much enhanced photocatalytic activity with good cycling stability. The significant enhancement in photoactivity is contributed to by both a high adsorption capacity and the separation efficiency of photo-generated electron-hole (e--h+) pairs via a Z-scheme mechanism. In addition, radical scavenging experiments confirm that the reactive ·OH radicals play an important role in the photocatalytic reaction. The novel (AB/BOB) heterojunction composites could have a promising application in treatment of various dyestuff wastewaters on a large scale.

Atom Diffusion and Evaporation of Free-Ended Amorphous SiOx Nanowires: Nanocurvature Effect and Beam-Induced Athermal Activation Effect.

Arresting effects of nanocurvature and electron beam-induced athermal activation on the structure changes at nanoscale of free-ended amorphous SiOx nanowire were demonstrated. It was observed that under in situ uniform electron beam irradiation in transmission electron microscope, the near surface atoms at the most curved free end of the nanowire preferentially vaporized or diffused to the less curved wire sidewall. The processing resulted in an intriguing axial shrinkage and an abnormal radial expansion of the wire. It was also observed that with the beam energy deposition rate being lowered, although both the diffusion and the evaporation slowed down, the processing transferred from an evaporation-dominated status to a diffusion-dominated status. These results are crucial not only to the fundamental understanding but also to the technical controlling of the electron beam-induced structure change at nanoscale or nanoprocessing of low dimensional nanostructures.

Intriguing surface-extruded plastic flow of SiOx amorphous nanowire as athermally induced by electron beam irradiation.

Nanoinstability and nanoprocessing of a SiOx amorphous nanowire at room temperature as induced by in situ electron beam irradiation in transmission electron microscopy are systematically investigated. It is demonstrated that in contrast to the crystalline nanowires where only the beam-induced ablation of atoms was observed, the amorphous nanowire herein can give rise to an arresting beam-induced surface-extruded plastic flow of massive atoms and surface migration of atoms in addition to the beam-induced ablation of atoms. Via the plastic flow and ablation, a new S-type deformed wire and the thinnest amorphous nanowire are elaborately created locally at nanoscale precision with a highly controllable manner depending on the beam current density, beam spot size, and beam position. The existing knock-on mechanism and simulation seem inadequate to explain these processes. However, it is indicated that a much higher nanocurved surface energy of nanowires and an enhanced beam-induced soft mode and instability of atomic vibration control the processes.