Fabrication process for picoliter volume SiO2 glass tube array partially embedded in Si wafer was developed. As a template for the glass tubes, macropore array was formed at the surface of n-Si(1 0 0) wafer by photo-assisted electrochemical etching process. The area-selective formation of the array was achieved by applying Au/Cr micropatterns formed at the back-side surface of the substrate as the shade mask, which controls the illumination condition to optimize the etching reaction conditions. Subsequently, surface of the macropores was wet-thermally oxidized to form glass layer, and the bulk Si region was removed by alkaline etching, remaining the "glass tubes". As a result of complete removal of the bulk Si, released glass tubes were obtained. By partial removal of the bulk Si part, the glass tubes were exposed, fixed in the remaining Si substrate in the form of well-ordered array. It was confirmed that the depth, the exposed region and the wall thickness of each glass tube were controllable by adjusting the parameters such as the duration of the Si electrochemical etching, the alkaline etching and the wet-thermal oxidation, respectively. In order to demonstrate microreaction in the glass tube, aqueous rhodamine B solution was injected into the tubes and excitation light was irradiated to them. As a result, the fluorescence of rhodamine B was clearly detected, confirming the applicability of the glass tubes for various kinds of devices and systems such as microreactors. (C) 2005 Elsevier Ltd. All rights reserved.