Pores in single crystalline semiconductors come in many forms (e.g., pore sizes from 2 nm to > 10 µm; morphologies from perfect pore crystal to fractal) and exhibit many unique properties directly or as nanocompounds if the pores are filled. The various kinds of pores obtained in semiconductors like Ge, Si, III-V, and II-VI compound semiconductors are systematically reviewed, emphasizing macropores. Essentials of pore formation mechanisms will be discussed, focusing on differences and some open questions but in particular on common properties. Possible applications of porous semiconductors, including for example high explosives, high efficiency electrodes for Li ion batteries, drug delivery systems, solar cells, thermoelectric elements and many novel electronic, optical or sensor devices, will be introduced and discussed.

Two different morphologies of porous layers were observed in (100)‐oriented anodically etched in an aqueous solution of . At high current density anodization leads to the formation of so‐called current‐line oriented pores. When the current density decreased to values lower than the morphology of the porous layers sharply changed and the pores began to grow along definite 〈111〉 crystallographic directions. ©2000 The Electrochemical Society

Cycling tests under various conditions have been performed for lithium ion battery anodes made from free-standing silicon microwires embedded at one end in a copper current collector. Optimum charging/discharging conditions have been found for which the anode shows negligible fading (< 0.001%) over 80 cycles; an outstanding result for this kind of anodes. Several performance parameters of the anode have been compared to the ones of other Si anode concepts, showing that especially the capacity as well as the rates of charge flow per nominal area of anode are the highest for the present anode. With regard to applications, the specific parameters per area are more important than the specific gravimetric parameters like the gravimetric capacity, which is good for comparing the capacity between materials but not enough for comparing between anodes.

The understanding of the mechanisms of macropore formation in p-type Si with respect to modulation of the pore diameter is still in its infancy. In the present work, macropores with significantly modulated diameters have been produced electrochemically in p-type Si. The effect of the current density and the amount of surfactant in the etching solution are shown to influence the modulation in pore diameter and morphology. Data obtained during the etching process by in situ FFT impedance spectroscopy correlate the pore diameter variation with certain time constants found in the kinetics of the dissolution process. Raman scattering and electron microscopy confirm the mesoscopic structure and roughening of the pore walls. Spectroscopic and microscopic methods confirm that the pore wall morphology is correlated with the conditions of pore modulation.

Silicon microwire arrays embedded in Cu present exceptional performance as anode material in Li ion batteries. The processes occurring during the first charging cycles of batteries with this anode are essential for good performance. This paper sheds light on the electrochemical and structural properties of the anodes during the first charging cycles. Scanning Electron Microscopy, X-ray diffractommetry, and fast Fourier transformation impedance spectroscopy are used for the characterization. It was found that crystalline phases with high Li content are obtained after the first lithiation cycle, while for the second lithiation just crystalline phases with less Li are observable, indicating that the lithiated wires become amorphous upon cycling. The formation of a solid electrolyte interface of around 250 nm during the first lithiation cycle is evidenced, and is considered a necessary component for the good cycling performance of the wires. Analog to voltammetric techniques, impedance spectroscopy is confirmed as a powerful tool to identify the formation of the different Si-Li phases.