From Microphase Separation to Self-Organized Mesoporous Phenolic Resin through Competitive Hydrogen Bonding with Double-Crystalline Diblock Copolymers of Poly(ethylene oxide-<i>b</i>-ε-caprolactone)

A series of immiscible crystalline–crystalline diblock copolymers, poly(ethylene oxide)-<i>b</i>-(ε-caprolactone) (PEO-<i>b</i>-PCL), were synthesized through ring-opening polymerization and then blended with phenolic resin. FT-IR analyses demonstrate that the ether group of PEO is a stronger hydrogen-bond acceptor with the hydroxyl group of phenolic resin than is the carbonyl group of PCL. Phenolic, after being cured with hexamethylenetetramine (HMTA), results in the excluded and confined PCL phase based on analyses by differential scanning calorimetry (DSC). This effect leads to the formation of a variety of composition-dependent nanostructures, including disorder, gyroid and short-cylinder structures. The self-organized mesoporous phenolic resin was found only at 40–60 wt % phenolic content by an intriguing balance of the contents of phenolic, PEO, and PCL. In addition, the mesoporous structure was destroyed at higher PCL/PEO ratios in the block copolymers, as determined by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) experiments. In addition, the large and long-range order of bicontinuous gyroid-type mesoporous carbon was obtained from mesoporous gyroid phenolic resin calcined at 800 °C under nitrogen

Palladium-Catalyzed Annulation of 2,2′-Diiodobiphenyls with Alkynes: Synthesis and Applications of Phenanthrenes

A range of phenanthrene derivatives were efficiently synthesized by the palladium-catalyzed annulation of 2,2′-diiodobiphenyls with alkynes. The scope, limitations and regioselectivity of the reaction were investigated. The described method was adopted to synthesize 9,10-dialkylphenanthrenes, sterically overcrowded 4,5-disubstituted phenanthrenes and phenanthrene-based alkaloids. Reactions of highly methoxy-substituted biphenyls with 2-(2-propynyl)­pyrrolidine and 2-(2-propynyl)­piperidine gave 2-(9-phenanthylmethyl)­pyrrolidines and 2-(9-phenanthylmethyl)­piperidines, respectively. The products were transformed to phenanthroindolizidine and phenanthroquinolizidine alkaloids by the Pictet–Spengler reaction

The Role of Ti Buffer Layer Thickness on the Resistive Switching Properties of Hafnium Oxide-Based Resistive Switching Memories

Ti/HfO_<i>x</i>-based resistive random access memory (RRAM) has been extensively investigated as an emerging nonvolatile memory (NVM) candidate due to its excellent memory performance and CMOS process compatibility. Although the importance of the role of the Ti buffer layer is well recognized, detailed understanding about the nature of Ti thickness-dependent asymmetric switching is still missing. To realize this, the present work addresses the effects of Ti buffer layer thickness on the switching properties of TiN/Ti/HfO_<i>x</i>/TiN 1T1R RRAM. Consequently, we have demonstrated a simple strategy to regulate the FORMING voltage, leakage current, memory window, and decrease the operation current, etc. by varying the thickness of the Ti layer on the HfO_<i>x</i> dielectrics. Accordingly, controllable and reliable bipolar, complementary, and reverse bipolar resistive switching (BRS, CRS, and R-BRS) properties have been demonstrated. This work also provides the direction to avoid unwanted CRS properties during the first RESET operation by decreasing the FORMING voltage. Furthermore, the memory device shows good nonvolatility at ∼1 μA programming current by selecting a proper thickness of Ti buffer layer. To achieve reliable BRS properties for low power application, the operation current has been further optimized, whereas the memory device shows pulse endurance of more than 7 million cycles at a low pulse width of 50 ns and excellent data retention properties of more than 40 h at 150 °C measurement temperature