A method of macro-porous silicon formation is proposed, which is based on silicon cathodic polarization in molten calcium chloride. It is assumed that the porosity formation is due to interaction of electrochemically reduced calcium metal with the silicon substrate. Surface architectures were composed of the pores up to 10 micrometers in thickness. High photoactivity of the samples was determined by photoelectrochemical measurements using white light and ethyl viologen as an electroactive agent. The proposed method offers new opportunities for silicon surface technologies, for instance, preparation of efficient electrodes for batteries and photoelectrochemical hydrogen generation as well as the platforms for sensors and antireflection coatings for photodevices.

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