Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium
There is provided a technique that includes: modifying a surface of first base exposed on a substrate by supplying modifying gas including the first base and second base exposed on the substrate; and selectively forming a film containing at least first element and second element different from the first element on a surface of the second base by supplying precursor gas to the substrate after the surface of the first base is modified, under condition that film-forming reaction by thermal decomposition of the precursor gas does not substantially occur, the precursor gas containing a compound in which atoms of the first element are contained in one molecule, at least one atom of the second element is interposed between two atoms of the first element, and each of the two atoms of the first element is directly bonded to one of the at least one atom of the second element.
1 . A method of processing a substrate, comprising:
(a) supplying a modifying gas to a substrate, which includes a first base and a second base on a surface of the substrate, to modify a surface of the first base that is terminated with a hydroxyl group; and
(b) forming a film containing at least a first element and a second element different from the first element on a surface of the second base by supplying a precursor gas to the substrate after the surface of the first base is modified, under a condition that a film-forming reaction by thermal decomposition of the precursor gas does not substantially occur, the precursor gas containing a compound in which two or more atoms of the first element are contained in one molecule, at least one atom of the second element is interposed between two atoms of the first element, and each of the two or more atoms of the first element is directly bonded to one of the at least one atom of the second element,
wherein in (a), a fluorine-containing gas and a silicon-containing gas are each used as the modifying gas, which modifies the surface of the first base to suppress the film from being formed on the modified surface of the first base,
wherein (a) includes:
(a1) supplying the silicon-containing gas to the substrate; and
(a2) supplying the fluorine-containing gas to the substrate, and
wherein (a1) and (a2) are performed in this order.
2 . The method of claim 1 , wherein the compound does not contain a bond between the atoms of the first element.
3 . The method of claim 1 , wherein the compound includes a structure in which the two or more atoms of the first element are directly bonded to one atom of the second element, or a structure in which the two or more atoms of the first element are directly bonded to two atoms of the second element bonded to each other respectively.
4 . The method of claim 1 , wherein in the compound, the first element is a semiconductor element or a metal element, and the second element is nitrogen, oxygen, or carbon.
5 . The method of claim 1 , wherein the compound is at least one selected from the group of compounds represented by formula (1) or (2):
X 3 A-Y-AX 3 (1)
X 3 A-Z-AX 2 -Z-AX 3 (2)
wherein, in the formulas (1) and (2), A is an atom of the first element represented by a silicon atom, a germanium atom, or a tetravalent metal atom; X represents a chlorine atom, a bromine atom, an iodine atom, NR 2 , or OR, independently; R represents a hydrogen atom or an alkyl group containing 1 to 5 carbon atoms, independently; Y represents NH, O, CH 2 , or CH 2 —CH 2 ; two Zs represent NH, O, or CH 2 , respectively; and in Y and Z, a nitrogen atom in NH, an oxygen atom in O, and carbon atoms in CH 2 and CH 2 —CH 2 are atoms of the second element.
6 . The method of claim 1 , wherein in the compound, the first element is silicon, the second element is nitrogen, oxygen, or carbon, and the compound contains at least one selected from the group of Si—N—Si bond, Si—N—Si—N—Si bond, Si—O—Si bond, Si—O—Si—O—Si bond, Si—C—Si bond, Si—C—Si—C—Si bond, and Si—C—C—Si bond.
7 . The method of claim 1 , wherein (b) includes:
performing a cycle a predetermined number of times, the cycle including:
(b1) supplying the precursor gas to the substrate; and
(b2) supplying a reaction gas including a molecular structure different from a molecular structure of the precursor gas to the substrate.
8 . The method of claim 1 , wherein in (a), the fluorine-containing gas as the modifying gas is used to terminate the surface of the first base with fluorine.
9 . The method of claim 8 , further comprising (c) removing fluorine termination formed on the surface of the first base after (b).
10 . The method of claim 1 , wherein an aminosilane-based gas is used as the silicon-containing gas.
11 . The method of claim 1 , wherein the silicon-containing gas is a gas of a compound containing one amino group in one molecule.
12 . The method of claim 1 , wherein the first base is an oxide film, and the second base is a film other than the oxide film.
13 . The method of claim 1 , wherein (a) and (b) are performed under a non-plasma atmosphere.
14 . A method of manufacturing a semiconductor device, comprising the method of claim 1 .