Time-varying wetting behavior on copper wafer treated by wet-etching

The wet cleaning process in semiconductor fabrication often involves the immersion of the copper wafer into etching solutions and thereby its surface properties are significantly altered. The wetting behavior of a copper film deposited on silicon wafer is investigated after a short dip in various etching solutions. The etchants include glacial acetic acid and dilute solutions of nitric acid, hydrofluoric acid, and tetramethylammonium hydroxide. It was found that in most cases a thin oxide layer still remains on the surface of as-received Cu wafers when they are subject to etching treatments. However, a pure Cu wafer can be obtained by the glacial acetic acid treatment and its water contact angle (CA) is about 45°. As the pure Cu wafer is placed in the ambient condition, the oxide thickness grows rapidly to the range of 10-20 Å within 3 h and the CA on the hydrophilic surface also rises. In the vacuum, it is surprising to find that the CA and surface roughness of the pure Cu wafer can grow significantly. These interesting results may be attributed to the rearrangement of surface Cu atoms to reduce the surface free energy.