Silicon microtubes made by immersing macroporous silicon into ammonium fluoride solution

In this paper, we report the fabrication of silicon microtubes (SMT) by electrochemical dissolution of macroporous silicon layers immersed into aqueous solution of NH4F mixed with Na2SO4, at different pH levels (4.5-9.5). Well-defined SMT have been obtained at pH 6.5, 7.5 and 9.5, whereas for other pH levels, the surface of the porous structure becomes passivated or formation of needle-like structure occurs. The mean inner diameter and the thickness of walls of the tubes shown to be depended on the pH level of the solutions. In this investigation, we obtained silicon tubes with inner diameter from 0.2 to 2.0 μm with thickness wall from about 0.23 to 0.50 μm. The investigation of these structures indicates that for tube formation the pH level and predominance of the anisotropic dissolution are necessary conditions. The tube formation cannot be explained regarding the silicon dissolution mechanism. For this aim, the role of the space charge region must be regarded. The structural characterization of silicon tubes was achieved by X-ray diffraction (XRD), X-ray energy dispersive Spectroscopy (EDS) and Raman spectroscopy and the results pointed out that these tubes are constituted by crystalline silicon structures covered by a very thin silicon oxide film. In this paper, the formation mechanism of the SMT is also discussed, highlighting the role of the space charge region (SCR) and the pH level for tube formation.