Method of manufacturing semiconductor device, substrate processing apparatus and non-transitory computer-readable recording medium
Provided is a method of manufacturing a semiconductor device, which is capable of increasing the controllability of the concentration of carbon in a film by increasing the yield when a boron carbonitride film or a boron nitride film is formed. The method includes forming a film containing boron, carbon and nitrogen or a film containing boron and nitrogen on the substrate by performing, a predetermined number of times, a cycle including supplying a source gas consisting of boron and a halogen element to a substrate and supplying a reactive gas consisting of carbon, nitrogen and hydrogen to the substrate.
1. A method of manufacturing a semiconductor device, comprising forming a film containing boron, carbon and nitrogen or a film containing boron and nitrogen on a substrate by performing, a predetermined number of times, a cycle comprising: (a) supplying a source gas comprising a molecule containing boron and a halogen element to the substrate; (b) supplying a reactive gas consisting of carbon, nitrogen and hydrogen to the substrate; and (c) supplying a nitriding gas to the substrate, wherein a first layer containing boron and the halogen element is formed in the step (a), a second layer containing boron, carbon and nitrogen is formed by reacting the first layer with the reactive gas in the step (b), and a third layer containing boron, carbon and nitrogen or containing boron and nitrogen is formed by nitriding the second layer in the step (c).
2. The method of claim 1 , wherein the reactive gas comprises at least one of amine and organic hydrazine.
3. The method of claim 1 , wherein the reactive gas comprises at least one amine selected from a group consisting of ethylamine, methylamine, propylamine, isopropylamine, butylamine and isobutylamine.
4. The method of claim 1 , wherein the reactive gas is boron-free.
5. The method of claim 1 , wherein the reactive gas is boron-free and metal-free.
6. The method of claim 1 , wherein the halogen element comprises one of chlorine and fluorine.
7. The method of claim 1 , wherein the halogen element in the source gas and hydrogen in the reactive gas are discharged in gaseous state when the film is formed.
8. The method of claim 1 , wherein in the step (b) the first layer reacts with the reactive gas, at least a portion of atoms of the halogen element in the first layer is drawn out from the first layer, at least a portion of ligands in the reactive gas is separated from the reactive gas, and nitrogen in the reactive gas with at least the portion of ligands separated therefrom is bonded to boron in the first layer.
9. The method of claim 1 , wherein the step (c) is performed in each cycle after alternately performing the steps (a) and (b) a predetermined number of times.
10. A substrate processing apparatus comprising:
a process chamber configured to accommodate a substrate;
a source gas supply system configured to supply a source gas comprising a molecule containing boron and a halogen element into the process chamber;
a reactive gas supply system configured to supply a reactive gas consisting of carbon, nitrogen and hydrogen into the process chamber;
a nitriding gas supply system configured to supply a nitriding gas into the process chamber; and
a controller configured to control the source gas supply system, the reactive gas supply system and the nitriding gas supply system to perform a formation of a film containing boron, carbon and nitrogen or a film containing boron and nitrogen on the substrate by performing, a predetermined number of times, a cycle comprising: supplying the source gas to the substrate in the process chamber to form a first layer containing boron and the halogen element; supplying the reactive gas to the substrate in the process chamber to form a second layer containing boron, carbon and nitrogen by reacting the first layer with the reactive gas; and supplying a nitriding gas to the substrate to form a third layer containing boron, carbon and nitrogen or containing boron and nitrogen by nitriding the second layer.
11. A non-transitory computer-readable recording medium storing a program that causes a computer to perform a formation of a film containing boron, carbon and nitrogen or a film containing boron and nitride on a substrate by performing, a predetermined number of times, a cycle comprising: supplying a source gas comprising a molecule containing boron and a halogen element to the substrate to form a first layer containing boron and the halogen element; supplying a reactive gas consisting of carbon, nitrogen and hydrogen to the substrate to form a second layer containing boron, carbon and nitrogen by reacting the first layer with the reactive gas; and supplying a nitriding gas to the substrate to form a third layer containing boron, carbon and nitrogen or containing boron and nitrogen by nitriding the second layer.