Method of manufacturing semiconductor device, method of processing substrate, substrate processing apparatus and non-transitory computer-readable recording medium

1. A method of manufacturing a semiconductor device, comprising:

forming a film on a substrate by performing a cycle a predetermined number of times, the cycle comprising:

supplying a raw material gas to a substrate in a process chamber;

exhausting the raw material gas remaining in the process chamber through an exhaust line in a state where the supply of the raw material gas is being stopped;

supplying an amine-based gas to the substrate in the process chamber; and

exhausting the amine-based gas remaining in the process chamber through the exhaust line in a state where the supply of the amine-based gas is being stopped,

wherein a degree of valve opening of an exhaust valve disposed in the exhaust line is changed in multiple steps in the act of exhausting the amine-based gas remaining in the process chamber.

2. The method of claim 1 , wherein the act of exhausting the amine-based gas remaining in the process chamber includes:

exhausting the amine-based gas remaining in the process chamber with the degree of valve opening as a first degree of valve opening; and

exhausting the amine-based gas remaining in the process chamber with the degree of valve opening as a second degree of valve opening which is higher than the first degree of valve opening.

3. The method of claim 2 , wherein the second degree of valve opening is fully-opened.

4. The method of claim 1 , wherein the act of exhausting the amine-based gas remaining in the process chamber includes continuously supplying an inert gas into the process chamber.

5. The method of claim 1 , wherein the raw material gas contains a halogen element.

6. The method of claim 1 , wherein the raw material gas contains a chlorine element or a fluorine element.

7. The method of claim 1 , wherein the raw material gas contains a chlorine element.

8. The method of claim 1 , wherein the amine-based gas contains amine.

9. The method of claim 1 , wherein the amine-based gas contains at least one amine selected from a group consisting of ethylamine, methylamine, propylamine, isopropylamine, butylamine and isobutylamine.

10. The method of claim 1 , wherein the amine-based gas contains at least one amine selected from a group consisting of triethylamine, diethylamine, monoethylamine, trimethylamine, dimethylamine, monomethylamine, tripropylamine, dipropylamine, monopropylamine, triisopropylamine, diisopropylamine, monoisopropylamine, tributylamine, dibutylamine, monobutylamine, triisobutylamine, diisobutylamine and monoisobutylamine.

11. The method of claim 1 , wherein the act of exhausting the amine-based gas remaining in the process chamber includes changing a set internal pressure of the process chamber in multiple steps.

12. The method of claim 11 , wherein the act of exhausting the amine-based gas remaining in the process chamber includes:

exhausting the amine-based gas remaining in the process chamber with the set internal pressure of the process chamber as a first set internal pressure; and

exhausting the amine-based gas remaining in the process chamber with the set internal pressure of the process chamber as a second set internal pressure which is lower than the first set internal pressure.

13. The method of claim 12 , wherein the act of exhausting the amine-based gas remaining in the process chamber with the set internal pressure of the process chamber as the second set internal pressure includes exhausting the amine-based gas with the maximum exhaust capability of the exhaust line.

14. The method of claim 1 , wherein the act of exhausting the amine-based gas remaining in the process chamber includes changing the exhaust capability of the exhaust line in multiple steps.

15. The method of claim 14 , wherein the act of exhausting the amine-based gas remaining in the process chamber includes:

exhausting the amine-based gas remaining in the process chamber with the exhaust capability of the exhaust line as a first exhaust capability; and

exhausting the amine-based gas remaining in the process chamber with the exhaust capability of the exhaust line as a second exhaust capability which is higher than the first exhaust capability.

16. The method of claim 15 , wherein the act of exhausting the amine-based gas remaining in the process chamber with the exhaust capability of the exhaust line as the second exhaust capability includes exhausting the amine-based gas with the maximum exhaust capability of the exhaust line.

17. A method of processing a substrate, comprising:

forming a film on the substrate by performing a cycle a predetermined number of times, the cycle comprising:

supplying a raw material gas to a substrate in a process chamber;

exhausting the raw material gas remaining in the process chamber through an exhaust line in a state where the supply of the raw material gas is being stopped;

supplying an amine-based gas to the substrate in the process chamber; and

exhausting the amine-based gas remaining in the process chamber through the exhaust line in a state where the supply of the amine-based gas is being stopped,

wherein a degree of valve opening of an exhaust valve disposed in the exhaust line is changed in multiple steps in the act of exhausting the amine-based gas remaining in the process chamber.

18. A substrate processing apparatus comprising:

a process chamber configured to accommodate a substrate;

a raw material gas supply system configured to supply a raw material gas to the substrate in the process chamber;

an amine-based gas supply system configured to supply an amine-based gas to the substrate in the process chamber;

an exhaust line configured to exhaust the interior of the process chamber;

an exhaust valve disposed in the exhaust line; and

a controller configured to control the raw material gas supply system, the amine-based gas supply system, the exhaust line and the exhaust valve such that a film is formed on the substrate by performing a cycle a predetermined number of times, the cycle comprising:

supplying the raw material gas to the substrate in the process chamber;

exhausting the raw material gas remaining in the process chamber through the exhaust line in a state where the supply of the raw material gas is being stopped;

supplying the amine-based gas to the substrate in the process chamber; and

exhausting the amine-based gas remaining in the process chamber through the exhaust line in a state where the supply of the amine-based gas is being stopped,

wherein a degree of valve opening of the exhaust valve is changed in multiple steps in the act of exhausting the amine-based gas remaining in the process chamber.

19. A non-transitory computer-readable recording medium storing a program that causes a computer to perform a process of forming a film on a substrate by performing a cycle a predetermined number of times, the cycle comprising:

supplying a raw material gas to a substrate in a process chamber;

exhausting the raw material gas remaining in the process chamber through an exhaust line in a state where the supply of the raw material gas is being stopped;

supplying an amine-based gas to the substrate in the process chamber; and

exhausting the amine-based gas remaining in the process chamber through the exhaust line in a state where the supply of the amine-based gas is being stopped,

wherein a degree of valve opening of an exhaust valve disposed in the exhaust line is changed in multiple steps in the act of exhausting the amine-based gas remaining in the process chamber.