Surface plasmonic coupling of Au nanoparticle arrays with ultrathin hexagonal boron nitride nanosheets for Raman enhancement.

Integration of hexagonal boron nitride (h-BN) with plasmonic nanostructures that possess nanoscale field confinement will enable unusual properties; hence, the manipulation and understanding of the light interactions are highly desirable. Here, we demonstrate the surface plasmonic coupling of Au nanoparticles (ANPs) with ultrathin h-BN nanosheets (BNNS) in nonspecific nanocomposites leading to a great enhancement of the Raman signal of E2g in both experimental and theoretical manner. The nanocomposites were fabricated from liquid-exfoliated atomically thin BNNS and diblock copolymer-based ANPs with excellent dispersion through a self-assembly approach. By precisely varying the size of ANPs from 3 to 9 nm, the Raman signal of BNNS was improved from 1.7 to 71. In addition, the underlying mechanism has been explored from the aspects of electromagnetic field coupling strength between the localized surface plasmons excited from ANPs and the surrounding dielectric h-BN layers, as well as the charge transfer at the BNNS/ANPs interfaces. Moreover, we also demonstrate its capability to detect dye molecules as a surface enhanced Raman scattering (SERS) substrate. This work provides a basis for the self-assembly of BNNS hierarchical nanocomposites allowing for plasmon-mediated modulation of their optoelectronic properties, thereby showing the great potential not only in the field of SERS but also in large-scale h-BN-based plasmonic devices.

Propulsion of Homonuclear Colloidal Chains Based on Orientation Control under Combined Electric and Magnetic Fields.

The remarkable efficiency and dynamics of micromachines in living organisms have inspired researchers to make artificial microrobots for targeted drug delivery, chemical sensing, cargo transport, and waste remediation applications. While several self- and directed-propulsion mechanisms have been discovered, the phoretic force has to be generated via either asymmetric surface functionalization or sophisticated geometric design of microrobots. As a result, many symmetric structures assembled from isotropic colloids are ruled out as viable microrobot possibilities. Here, we propose to utilize orientation control to actuate axially symmetric micro-objects with homogeneous surface properties, such as linear chains assembled from superparamagnetic microspheres. We demonstrate that the fore-and-aft symmetry of a horizontal chain can be broken by tilting it with an angle relative to the substrate under a two-dimensional magnetic field. A superimposed alternating current electric field propels the tilted chains. Our experiments and numerical simulation confirm that the electrohydrodynamic flow along the electrode is unbalanced surrounding the tilted chain, generating hydrodynamic stresses that both propel the chain and reorient it slightly toward the substrate. Our work takes advantage of external fields, where the magnetic field, as a driving wheel and brake, controls chain orientation and direction, while the electric field, as an engine, provides power for locomotion. Without the need to create complex-shaped micromotors with intricate building blocks, our work reveals a propulsion mechanism that breaks the symmetry of hydrodynamic flow by manipulating the orientation of a microscopic object.

Enhancement ofn-type conductivity of hexagonal boron nitride films byin-situco-doping of silicon and oxygen.

Effective doping of ultra-wide band gap semiconductors is of crucial importance, yet, remains challenging. Here, we report the enhancement ofn-type conductivity of nanocrystalline hexagonal boron nitride (h-BN) films with simultaneous incorporation of Si and O while deposition by radio frequency magnetron sputtering method. The resultanth-BN films are of ∼50 nm in thickness, containing nitrogen vacancy (VN) defects. Incorporation of O together with Si results in effective healing of VNdefects and significantly reduces electric resistivity inh-BN thin films. X-ray photoelectron spectroscopy results reveal that under B-rich condition, the substitutional O in VNbonding with B leads to the formation of Si-N, which thus plays an important role to then-type conductivity inh-BN films. The temperature dependent electrical resistivity measurements of the Si/O co-dopedh-BN films reveal two donor levels of 130 and 520 meV at room temperature and higher temperatures, respectively. Then-h-BN/p-Si heterojunctions demonstrate apparent rectification characteristics at room temperature, where the tunneling behavior dominates throughout the injection regimes due to the effective carrier doping. This work proposes an effective approach to enhance then-type conductivity ofh-BN thin films for future applications in electronics, optoelectronics and photovoltaics.

Synthesis and Propulsion of Magnetic Dimers under Orthogonally Applied Electric and Magnetic Fields.

Anisotropic particles have been widely used to make micro/nanomotors that convert chemical, ultrasonic, electrical, or magnetic energy into mechanical energy. The moving directions of most colloidal motors are, however, difficult to control. For example, asymmetric dimers with two lobes of different sizes, ζ-potential, or chemical composition have shown rich propulsion behaviors under alternating current (AC) electric fields due to unbalanced electrohydrodynamic flow. While they always propel in a direction perpendicular to the applied electric field, their moving directions along the substrate are hard to control, limiting their applications for cargo delivery. Inspired by two separate engine and steering wheel systems in automobiles, we use orthogonally applied AC electric field and direct current (DC) magnetic field to control the dimer's speed and direction independently. To this end, we first synthesize magnetic dimers by coating dopamine-functionalized nanoparticles on geometrically asymmetric polystyrene dimers. We further characterize their static and dynamic susceptibilities by measuring the hysteresis diagram and rotation speed experimentally and comparing them with theoretical predictions. The synthesized dimers align their long axes quickly with a planar DC magnetic field, allowing us to control the particles' orientation accurately. The propulsion speed of the dimers, on the other hand, is tunable by an AC electric field applied perpendicularly to the substrate. As a result, we can direct the particle's motion with predesigned trajectories of complex shapes. Our bulk-synthesis approach has the potential to make other types of magnetically anisotropic particles. And the combination of electric and magnetic fields will help pave the way for the assembly of magnetically anisotropic particles into complex structures.

Highly Transparent Crosslinkable Radical Copolymer Thin Film as the Ion Storage Layer in Organic Electrochromic Devices.

A highly transparent crosslinkable thin film made of the radical polymer poly(2,2,6,6-tetramethyl-4-piperidinyloxy methacrylate)- co-(4-benzoylphenyl methacrylate) (PTMA- co-BP) has been developed as the ion storage layer in electrochromic devices (ECDs). After photo-crosslinking, the dissolution of PTMA- co-BP in electrolytes was mitigated, which results in an enhanced electrochemical stability compared with the homopolymer PTMA thin film. Moreover, the redox capacity of PTMA- co-BP increased because of the formation of a crosslinked network. By matching the redox capacity of the PTMA- co-BP thin film and bis(alkoxy)-substituted poly(propylenedioxythiophene), the ECD achieved an optical contrast of 72% in a small potential window of 2.55 V (i.e., switching between +1.2 and -1.35 V), and it was cycled up to 1800 cycles. The ECD showed an excellent optical memory as its transmittance decayed by less than 3% in both the colored and bleached states while operating for over 30 min under open-circuit conditions. Use of crosslinkable radical polymers as the transparent ion storage layer opens up a new venue for the fabrication of transmissive-mode organic ECDs.