F4-TCNQ on Epitaxial Bi-Layer Graphene: Concentration- and Orientation-Dependent Charge Transfer at the Interface.

Bi-layer epitaxial graphene (BLG) on 6H-SiC(0001) (EG/SiC) was grown and modified by thermal deposition of the molecular electron acceptor tetrafluoro-tetra cyano quinodimethane (F4-TCNQ). The surface-modified system, F4-TCNQ/EG/SiC, was studied by X-ray photoelectron spectroscopy (XPS) and angle-resolved polarized Raman spectroscopy (ARPRS). XPS results indicate that bonding of deposited F4-TCNQ molecules depends on their concentration. Although bonding through the cyano groups is present at all concentrations, charge transfer from graphene to fluorine is evident only at sub-monolayer concentrations. The corresponding change in bond character is coupled with a change in molecular orientation. Raman spectroscopy not only provides results consistent with the findings from the XPS study but also reveals a significant degree of molecular stacking above the monolayer concentration. Thus, both the variation of the acceptor concentration and the number of graphene layers provide further handles to manipulate charge and doping that may be useful in device applications.

Achieving a High Thermally Conductive One Micron AlN Deposition by High Power Impulse Magnetron Sputtering plus Kick.

High-power impulse magnetron sputtering (HiPIMS) plus kick is a physical vapor deposition method that employs bipolar microsecond-scale voltage pulsing to precisely control the ion energy during sputter deposition. HiPIMS plus kick for AlN deposition is difficult since nitride deposition is challenged by low surface diffusion and high susceptibility to ion damage. In this current study, a systematic examination of the process parameters of HiPIMS plus kick was conducted. Under optimized main negative pulsing conditions, this study documented that a 25 V positive kick biasing for AlN deposition is ideal for optimizing a high quality film, as shown by X-ray diffraction and transmission electron microscopy as well as optimal thermal conductivity while increasing high speed deposition (25 nm/min) and obtaining ultrasmooth surfaces (rms roughness = 0.5 nm). HiPIMS plus kick was employed to deposit a single-texture 1 µm AlN film with a 7.4° rocking curve, indicating well oriented grains, which correlated with high thermal conductivity (121 W/m·K). The data are consistent with the optimal kick voltage enabling enhanced surface diffusion due to ion-substrate collisions without damaging the AlN grains.

Target-Specific Superparamagnetic Hydrogel with Excellent pH Sensitivity and Reversibility: A Promising Platform for Biomedical Applications.

Superparamagnetism has been widely used for many biomedical applications, such as early detection of inflammatory cancer and diabetes, magnetic resonance imaging (MRI), hyperthermia, etc., whereas incorporation of superparamagnetism in stimulus-responsive hydrogels has now gained substantial interest and attention for application in these fields. Recently, pH-responsive superparamagnetic hydrogels showing the potential use in disease diagnosis, biosensors, polymeric drug carriers, and implantable devices, have been developed based on the fact that pH is an important environmental factor in the body and some disease states manifest themselves by a change in the pH value. However, improvement in pH sensitivity of magnetic hydrogels is a dire need for their practical applications. In this study, we report the distinctly high pH sensitivity of new synthesized dual-responsive magnetic hydrogel nanocomposites, which was accomplished by copolymerization (free-radical polymerization) of two pH-sensitive monomers, acrylic acid (AA) and vinylsulfonic acid (VSA) with an optimum ratio, in the presence of presynthesized superparamagnetic iron oxide nanoparticles (Fe3O4(OH) x ). The monomers contain pH-sensitive functional groups (COO- and SO3 - for AA and VSA, respectively), and they have also been widely used as biomaterials because of the good biocompatibility. The pH sensitivity of the superparamagnetic hydrogel, poly(acrylic acid-co-vinylsulfonic acid), PAAVSA/Fe3O4, was investigated by swelling studies at different pH values from pH 7 to 1.4. Distinct pH reversibility of the system was also demonstrated through swelling/deswelling analysis. Thermal stability, chemical configuration, magnetic response, and structural properties of the system have been explored by suitable characterization techniques. Furthermore, the study reveals a pH-responsive significant change in the overall morphology and packing fraction of iron oxide nanoparticles in PAAVSA/Fe3O4 via energy-dispersive X-ray (EDX) elemental mapping with the field emission scanning electron microscopy (FESEM) study (for freeze-dried PAAVSA/Fe3O4, swelled at different pH values), implying a drastic change in susceptibility and induced saturation magnetization of the system. These important features could be easily utilized for the purpose of diagnosis using magnetic probe and/or impedance analysis techniques.