Transmission electron microscopy analysis of self-ordered porous alumina obtained by electrochemical anodization shows that self-ordering requires a porosity of 10%, independent of the specific anodization conditions. This corresponds to a volume expansion of alumina to aluminum of about 1.2. We propose that self-ordering of porous alumina with any interpore distance is possible if the applied potential, which mainly determines the interpore distance, and the pH value of the electrolyte, which mainly defines the pore radius, match the 10% porosity rule.

Self-ordering Regimes of Porous Alumina: The 10% Porosity Rule

Applying metamaterial concepts to dielectric systems offers low losses compared with metallic structures. Here, silicon-based metamaterial and nanophotonic advances are reviewed. The prospect of creating metamaterials with optical properties greatly exceeding the parameter space accessible with natural materials has been inspiring intense research efforts in nanophotonics for more than a decade. Following an era of plasmonic metamaterials, low-loss dielectric nanostructures have recently moved into the focus of metamaterial-related research. This development was mainly triggered by the experimental observation of electric and magnetic multipolar Mie-type resonances in high-refractive-index dielectric nanoparticles. Silicon in particular has emerged as a popular material choice, due to not only its high refractive index and very low absorption losses in the telecom spectral range, but also its paramount technological relevance. This Review overviews recent progress on metamaterial-inspired silicon nanostructures, including Mie-resonant and off-resonant regimes.

Metamaterial-inspired silicon nanophotonics

A review of experimental work on freezing and melting in confinement is presented. A range of systems, from metal oxide gels to porous glasses to novel nanoporous materials, is discussed. Features such as melting-point depression, hysteresis between freezing and melting, modifications to bulk solid structure and solid-solid transitions are reviewed for substances such as helium, organic fluids, water and metals. Recent work with well characterized assemblies of cylindrical pores like MCM-41 and graphitic microfibres with slit pores has suggested that the macroscopic picture of melting and freezing breaks down in pores of molecular dimensions. Applications of the surface force apparatus to the study of freezing and melting phenomena in confinement are discussed in some detail. This instrument is unique in allowing the study of conditions in a single pore, without the complications of pore blockage and connectivity effects. The results have confirmed the classical picture of melting-point depression in larger pores, and allowed the direct observation of capillary condensation of solid from vapour. Other results include the measurement of solvation forces across apparently fluid films below the bulk melting point and a solid-like response to shear of films above the bulk melting point. These somewhat contradictory findings highlight the difficulty of using bulk concepts to define the phase state of a substance confined to nanoscale pores.

https://iopscience.iop.org/article/10.1088/0953-8984/13/11/201/pdf

Confinement effects on freezing and melting

In an effort to maximize the liquid slip on superhydrophobic surfaces, we investigate the role of the nanoscale roughness on microscale structures by developing well-defined micro−nano hierarchical...

Maximizing the giant liquid slip on superhydrophobic microstructures by nanostructuring their sidewalls.

Spatial confinement in nanoporous media affects the structure, thermodynamics and mobility of molecular soft matter often markedly. This article reviews thermodynamic equilibrium phenomena, such as physisorption, capillary condensation, crystallisation, self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equilibrium physics, i.e. the rheology of liquids, capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined molecular species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcohols to liquid crystals, polymers, ionic liquids, proteins and water. Mostly, experiments with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diameters ranging from a few up to 50 nm are presented. The observed peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystallisation in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnological importance, e.g. for the synthesis of organic/inorganic hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochemical deposition of nano structures.

https://iopscience.iop.org/article/10.1088/0953-8984/27/10/103102/pdf

Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media

Electrochemical pore formation in silicon electrodes is a well-known phenomenon. While micropore formation is commonly understood as due to quantum size effects, the formation of larger pores is dominated by the electric field of the space charge region. In contrast to the macropore regime which is well understood, little is known about the morphology and formation mechanism of mesopores. In this report mesopore morphology and its dependence on formation parameters, such as HF concentration, current density, bias, and substrate doping density, is investigated in detail. In addition, a simulation of the breakdown conditions at the pore tip is performed which shows that mesopore formation is dominated by charge carrier tunneling, while avalanche breakdown is found to be responsible for the formation of large etchpits.

R Stengl

Papers

On the morphology and the electrochemical formation mechanism of mesoporous silicon