Substrate processing method

A substrate processing method to process a substrate having a major surface at which a pattern having a concave portion is formed, the substrate processing method comprising:

• performing a water-repellent treatment on the major surface of the substrate to supply a water repellent agent-containing liquid to the major surface of the substrate and to change a contact angle of pure water with respect to a flat surface to 90° or greater;
• after performing the water-repellent treatment on the major surface of the substrate, supplying a hydrophobic liquid to the major surface of the substrate and replacing the water repellent agent-containing liquid on the major surface of the substrate with the hydrophobic liquid;
• after supplying the hydrophobic liquid to the major surface of the substrate, supplying a hydrophilic liquid that is mixable with the hydrophobic liquid and that has hydrophilicity higher than the hydrophobic liquid to the major surface of the substrate and replacing the hydrophobic liquid on the major surface of the substrate with the hydrophilic liquid to form a liquid film of the hydrophilic liquid on the major surface of the substrate;
• and
• forming an opening that exposes the major surface in the liquid film by supplying a gas toward the liquid film and excluding the hydrophilic liquid from the major surface of the substrate by enlarging the opening;
• wherein, replacing the water repellent agent-containing liquid on the major surface of the substrate with the hydrophobic liquid includes filling the hydrophobic liquid into the concave portion of the pattern,
• replacing the hydrophobic liquid on the major surface of the substrate with the hydrophilic liquid includes:
• allowing the hydrophilic liquid to enter the concave portion while the hydrophilic liquid is mixed with the hydrophobic liquid in the concave portion by allowing the hydrophilic liquid to be supplied to the major surface of the substrate;
• and
• causing an internal liquid to recede from the concave portion by causing the internal liquid, which is a liquid in the concave portion, to flow;
• the substrate processing method further comprises promoting a retreat of the internal liquid from an inside of the concave portion, which is caused by a flow of the internal liquid, by giving external stimulation to the hydrophilic liquid on the major surface of the substrate, and
• the external stimulation is selected from the group consisting of (a), (b), and (c):
• (a) supplying the hydrophilic liquid that is in a droplet state;
• (b) changing a posture of the substrate;
• and
• (c) suctioning the liquid film by a suction nozzle.