Fabrication of Nanoscale Oxide Textured Surfaces on Polymers.

Nanoscale textured surfaces play an important role in creating antibacterial surfaces, broadband anti-reflective properties, and super-hydrophobicity in many technological systems. Creating nanoscale oxide textures on polymer substrates for applications such as ophthalmic lenses and flexible electronics imposes additional challenges over conventional nanofabrication processes since polymer substrates are typically temperature-sensitive and chemically reactive. In this study, we investigated and developed nanofabrication methodologies to create highly ordered oxide nanostructures on top of polymer substrates without any lithography process. We developed suitable block copolymer self-assembly, sequential infiltration synthesis (SIS), and reactive ion etching (RIE) for processes on polymer substrates. Importantly, to prevent damage to the temperature-sensitive polymer and polymer/oxide interface, we developed the process to be entirely performed at low temperatures, that is, below 80 °C, using a combination of UV crosslinking, solvent annealing, and modified SIS and RIE processes. In addition, we developed a substrate passivation process to overcome reactivity between the polymer substrate and the SIS precursors as well as a high precision RIE process to enable deep etching into the thermally insulated substrate. These methodologies widen the possibilities of nanofabrication on polymers.

Metal Oxide Heterostructure Array via Spatially Controlled-Growth within Block Copolymer Templates.

Nanofabrication is continuously searching for new methodologies to fabricate 3D nanostructures with 3D control over their chemical composition. A new approach for heterostructure nanorod array fabrication through spatially controlled-growth of multiple metal oxides within block copolymer (BCP) templates is presented. Selective growth of metal oxides within the cylindrical polymer domains of polystyrene-block-poly methyl methacrylate is performed using sequential infiltration synthesis (SIS). Tuning the diffusion of trimethyl aluminum and diethyl zinc organometallic precursors in the BCP film directs the growth of AlOx and ZnO to different locations within the cylindrical BCP domains, in a single SIS process. BCP removal yields an AlOx -ZnO heterostructure nanorods array, as corroborated by 3D characterization with scanning transmission electron microscopy (STEM) tomography and a combination of STEM and energy-dispersive X-ray spectroscopy tomography. The strategy presented here will open up new routes for complex 3D nanostructure fabrication.

Tin oxide nanostructure fabrication via sequential infiltration synthesis in block copolymer thin films.

Tin oxide (SnO2) nanostructures are attractive for sensing, catalysis, and optoelectronic applications. Here we investigate the fabrication of SnOx nanostructures through sequential infiltration synthesis (SIS) in block copolymer (BCP) film templates. While the growth of metal and metal oxides within polymers and BCP films via SIS has been demonstrated until now using small precursors such as trimethyl aluminum and diethyl zinc, we hypothesize that SIS can be performed using larger precursors and demonstrate SnOx SIS with tetrakis(dimethylamino)tin (TDMASn) and hydrogen peroxide. Tuning the SIS reaction and BCP chemistry resulted in highly ordered, polystyrene-block-poly(2-vinyl pyridine) (P2VP)-templated porous SnOx - AlOx and SnOx nanostructures. Detailed investigation using in-situ microbalance, high resolution electron microscopy, elemental analysis and infra-red spectroscopy shows that SnOx can directly grow within P2VP homopolymer and BCP films. Simultaneously with the growth, SnOx SIS process also contributes to the polymer etch. Performing SnOx SIS with pretreatment of a single AlOx SIS cycle increases the SnOx growth and protects the BCP template from etching. This is the first report of SnOx SIS opening a pathway for additional tetrakis-based organometallic precursors to be utilized in growth processes within polymers.

Role of interparticle interactions on microstructural and rheological properties of cellulose nanocrystal stabilized emulsions.

HYPOTHESIS: Microstructural and rheological properties of particle-stabilized emulsions are highly influenced by the nanoparticle properties such as size and surface charge. Surface charge of colloidal particles not only influences the interfacial adsorption but also the interparticle network formed by the non-adsorbed particles in the continuous phase. EXPERIMENTS: We have studied oil-in-water emulsions stabilized by cellulose nanocrystals (CNCs) with two different degrees of surface charge. Surface charge was varied by means of acidic or basic desulfation. Confocal microscopy coupled with rheology as well as cryogenic scanning electron microscopy were employed to establish a precise link between the microstructure and rheological behavior of the emulsions. FINDINGS: CNCs desulfated with hydrochloric acid (a-CNCs) were highly aggregated in water and shown to adsorb faster to the oil-water interface, yielding emulsions with smaller droplet sizes and a thicker CNC interfacial layer. CNCs desulfated using sodium hydroxide (b-CNCs) stabilized larger emulsion droplets and had a higher amount of non-adsorbed CNCs in the water phase. Rheological measurements showed that emulsions stabilized by a-CNCs formed a stronger network than for b-CNC stabilized emulsions due to increased van der Waals and H-bonding interactions that were not impeded by electrostatic repulsion.

Recent Advances in Mechanism Research and Methods for Electric-Field-Assisted Sintering of Ceramics.

Electric-field-assisted sintering of ceramic materials is under considerable attention during recent years. The current research is reviewed with a focus on mechanism research. Research of the mass transfer mechanisms in flash sintering (FS) is under debate during recent years. The research yields three main proposed mechanisms: nucleation due to movement of charged defects, Joule heating runaway, and electrochemical reactions. These are critically presented and discussed. Unlike FS, the mechanism of field-assisted sintering technologies (FAST) of ceramics is well agreed upon. However, recent studies challenge even this perception with new approaches, which are presented here. New technological and methodological developments in both FS and FAST/spark plasma sintering are also presented.