Method for forming carbon-containing silicon/metal oxide or nitride film by ALD using silicon precursor and hydrocarbon precursor

A method for forming a target film, other than a nitride film, containing carbon, oxygen, and silicon in a trench on a substrate placed in a reaction space by a process of atomic layer deposition (ALD) continuously repeating a deposition cycle throughout the process of ALD until the target film is formed, each deposition cycle forming a monolayer comprising steps of:

• (i) feeding a first precursor in a first pulse to the reaction space to adsorb the first precursor on the substrate, said first precursor containing silicon, and a first functional group selected from the group consisting of a first halogen group, and —NR12, wherein each R1 independently represents hydrogen or hydrocarbon group;
• (ii) feeding a second precursor in a second pulse to the reaction space to adsorb the second precursor on the substrate, said second precursor having no —NR22 and containing carbon but neither silicon nor metal, and a second functional group which is —OR2, wherein each R2 independently represents hydrogen or hydrocarbon group, wherein the first and second functional groups are a combination of the first halogen group and the —OR2, or the —NR12 and the —OR2,
• wherein each deposition cycle further comprising a purging step immediately following step (i), said purging step being immediately followed by step (ii),
• wherein (1) the first precursor is stored in liquid form in a first bottle, and is fed in the first pulse to the reaction space using a first flow-pass system (FPS) or a first bottle-out control system (BTO), wherein (1a) the first BTO is operated in a manner that a gas phase of the first precursor, while flowing from the first bottle, is merged into a flow of carrier gas upstream of the reaction space only when a vapor pressure of the first precursor inside the first bottle is higher than a pressure of the flow of carrier gas where the first precursor is merged into the flow of carrier gas wherein the carrier gas carries the gas phase of the first precursor without entering the first bottle throughout the step (i), or (1b) the first FPS is operated in a manner that the carrier gas flows continuously throughout the step (i) wherein the carrier gas carries the gas phase of the first precursor by passing through the first bottle, whereas being redirected to bypass the first bottle when not carrying the gas phase of the first precursor;
• and also (2) the second precursor is stored in liquid form in a second bottle, and is fed in the second pulse to the reaction space using a second flow-pass system (FPS) or a second bottle-out control system (BTO), wherein (2a) the second BTO is operated in a manner that a gas phase of the second precursor, while flowing from the second bottle, is merged into a flow of carrier gas upstream of the reaction space only when a vapor pressure of the second precursor inside the second bottle is higher than a pressure of the flow of carrier gas where the second precursor is merged into the flow of carrier gas wherein the carrier gas carries the gas phase of the second precursor without entering the second bottle throughout the step (ii), or (2b) the second FPS is operated in a manner that the carrier gas flows continuously throughout the step (ii) wherein the carrier gas carries the gas phase of the second precursor by passing through the second bottle, whereas being redirected to bypass the second bottle when not carrying the gas phase of the second precursor,
• wherein the first precursor together with the carrier gas is fed in the first pulse created by a first pulsing valve to the reaction space via a first auto pressure regulator (APR) without using a mass flow controller (MFC) wherein the first APR is provided upstream of the first pulsing valve, and the second precursor together with the carrier gas is fed in the second pulse created by a second pulsing valve to the reaction space via a second auto pressure regulator (APR) without using a mass flow controller (MFC) wherein the second auto pressure regulator is provided upstream of the second pulsing valve,
• and
• (iii) forming a monolayer constituting a portion of the target film containing carbon, oxygen, and silicon on the substrate by undergoing a substitution reaction between the first and second functional groups of the first and second precursors adsorbed on the substrate,
• wherein as a result of repeating the steps (i) to (iii), each said monolayer accumulates thereby constituting the target film.