A resist film is first formed on a substrate. Subsequently, a barrier film including a basic compound of, for example, dicyclohexylamine is formed on the resist film. Thereafter, with an immersion liquid including cesium sulfate provided on the barrier film, pattern exposure is carried out by selectively irradiating the resist film with exposing light through the barrier film. Then, after removing the barrier film, the resist film having been subjected to the pattern exposure is developed, so as to form a resist pattern in a good shape.