To form a fine pattern with a favorable profile by improving solubility (easy removing property) of a barrier film when the film is to be removed in immersion lithography.

A resist film 102 is formed on a substrate, and successively a barrier film 103 containing a plasticizer is formed on the resist film 102. Then, the resist film 102 is selectively irradiated with exposure light 105 through the barrier film 103 while a liquid 104 is present on the barrier film 103, thereby pattern exposure is performed. After the barrier film 102 is removed, the resist film 102 subjected to pattern exposure is developed to form a resist pattern 102a having a favorable profile without leaving a residue.