Method of manufacturing semiconductor device, method of processing substrate, substrate processing apparatus, and recording medium
There is provided a technique that includes forming a film containing a first element and oxygen on a substrate by performing a cycle a predetermined number of times, the cycle including: (a) supplying a modifying agent to the substrate to form, on the substrate, an adsorption layer containing the modifying agent physically adsorbed on a surface of the substrate; (b) supplying a precursor containing the first element to the substrate and causing the precursor to react with the surface of the substrate to form a first layer containing the first element on the substrate; and (c) supplying an oxidizing agent to the substrate and causing the oxidizing agent to react with the first layer to modify the first layer into a second layer containing the first element and oxygen.
1 . A method of processing a substrate, comprising
forming a film containing a first element and oxygen on the substrate by performing a cycle a predetermined number of times, the cycle including:
(a) supplying a modifying agent to the substrate to form an adsorption layer containing the modifying agent physically adsorbed on a portion of a surface of the substrate;
(b) supplying a precursor including a molecule containing the first element and ligand bonded to the first element to the substrate and causing the precursor to react with another portion of the surface of the substrate to form a first layer containing the first element while a first by-product containing the ligand desorbed from the first element in the precursor, which is generated during the formation of the first layer, is adsorbed on the adsorption layer; and
(c) supplying an oxidizing agent to the substrate and causing the oxidizing agent to react with the first layer to modify the first layer into a second layer containing the first element and oxygen.
2 . The method of claim 1 , wherein the first by-product contains the ligand desorbed from the first element in the precursor by a reaction between the precursor and an adsorption site on the surface of the substrate.
3 . The method of claim 1 , wherein adsorption of a second by-product, which contains the ligand desorbed from the first layer during formation of the second layer, on at least one selected from the group of the second layer and the surface of the substrate is suppressed by the adsorption layer.
4 . The method of claim 3 , wherein the adsorption layer suppresses adsorption of the second by-product on at least one selected from the group of the second layer and the surface of the substrate by adsorbing the second by-product on the adsorption layer in (c).
5 . The method of claim 3 , wherein (c) further includes (c2) exhausting a space in which the substrate is placed after supplying the oxidizing agent to the substrate, and
wherein in (c2), the second by-product that is adsorbed on the adsorption layer is removed from the surface of the substrate together with the modifying agent contained in the adsorption layer.
6 . The method of claim 1 , wherein the adsorption layer contains the modifying agent adsorbed to discontinuously cover the surface of the substrate.
7 . The method of claim 1 , wherein (a) further includes (a2) exhausting a space in which the substrate is placed after supplying the modifying agent to the substrate.
8 . The method of claim 7 , wherein in (a2), a portion of the modifying agent contained in the adsorption layer is removed from the surface of the substrate until a thickness of the adsorption layer decreases to a desired thickness so as to regulate a formation rate of the film to be a desired value in each cycle.
9 . The method of claim 7 , wherein in (a2), exhaust of the space in which the substrate is placed is continued until a thickness of the adsorption layer reaches a desired thickness.
10 . The method of claim 7 , wherein in (a2), an exhaust condition of the space in which the substrate is placed is set such that a formation rate of the film becomes a desired value.
11 . The method of claim 1 , wherein a concave structure is formed on the substrate, and the film is formed on an inner surface of the concave structure.
12 . The method of claim 11 , wherein in (a), the adsorption layer is formed on at least a bottom surface and a side wall of the inner surface of the concave structure.
13 . The method of claim 1 , wherein in (b), a precursor supply cycle is performed a plurality of times, the precursor supply cycle including:
supplying the precursor to the substrate; and
exhausting a space in which the substrate is placed with the supply of the precursor stopped.
14 . The method of claim 1 , wherein the modifying agent includes an organic compound.
15 . The method of claim 14 , wherein the modifying agent includes at least one selected from the group of an ether compound, a ketone compound, an amine compound, and an organic hydrazine compound.
16 . The method of claim 1 , wherein the ligand is an organic ligand.
17 . A method of manufacturing a semiconductor device, comprising the method of claim 1 .
18 . The method of claim 1 , wherein the adsorption layer suppresses adsorption of the first by-product on at least one selected from the group of the first layer and the surface of the substrate by adsorbing the first by-product on the adsorption layer in (b).
19 . The method of claim 1 , wherein (b) further includes (b2) exhausting a space in which the substrate is placed after supplying the precursor to the substrate, and
wherein in (b2), the first by-product that is adsorbed on the adsorption layer is removed from the surface of the substrate together with the modifying agent contained in the adsorption layer.