Method of forming a barrier film and method of forming wiring structure and electrodes of semiconductor device having a barrier film

A method of forming a film with ALD using a chemical vapor deposition apparatus comprising (i) a processing vessel, (ii) a mounting member which is provided in the processing vessel and supports a substrate thereon, (iii) heating means which heat the substrate supported by the mounting member, (iv) gas supply means having a plurality of gas spray ports for spraying gas onto the substrate in the process vessel, (v) evacuating means for evacuating the gas in the processing vessel so that the gas sprayed onto the substrate flows downwardly, (vi) a first gas source for storing a first process gas, (vii) a second gas source for storing a second process gas, (viii) a third gas source for storing an inert gas, (ix) a first gas introducing pipe which connects the first gas source to the gas supply means, and (x) a second gas introducing pipe which connects the second gas source to the gas supply means, at least one of the first and second gas introducing pipes connecting the third gas source to the gas supply means,

• the method comprising of:
• a first step of supplying the first process gas from the first gas source through the first gas introducing pipe to and through the gas supply means onto the substrate within the processing vessel;
• a second step of supplying the second process gas from the second gas source through the second gas introducing pipe to and through the gas supply means onto the substrate to reduce the first process gas supplied to the substrate, thereby forming a film on the substrate;
• a third step of purging the processing vessel by evacuating the processing vessel while supplying the inert gas from the third gas source into the processing vessel through said at least one of the first and second gas introducing pipes and the gas supply means,
• wherein the first and second steps are repeated at least once with the third step of purging being carried out between each of the first and second steps and between the second step and the first step of the repetition of the first and second steps such that the third step reduces residual gas remaining after performing the first and second steps to a level of 1 to 30% based on the entire capacity of the processing vessel.

A method of forming a film with ALD using a chemical vapor deposition apparatus comprising (i) a processing vessel, (ii) a mounting member which is provided in the processing vessel and supports a substrate thereon, (iii) heating means which heat the substrate supported by the mounting member, (iv) gas supply means having a plurality of gas spray ports for spraying gas onto the substrate in the process vessel, (v) evacuating means for evacuating the gas in the processing vessel so that the gas sprayed onto the substrate flows downwardly, (vi) a first gas source for storing a first process gas, (vii) a second gas source for storing a second process gas, (viii) a third gas source for storing an inert gas, (ix) a first gas introducing pipe which connects the first gas source to the gas supply means, and (x) a second gas introducing pipe which connects the second gas source to the gas supply means, at least one of the first and second gas introducing pipes connecting the third gas source to the gas supply means,

• the method comprising of:
• a first step of supplying the first process gas from the first gas source through the first gas introducing pipe to and through the gas supply means onto the substrate within the processing vessel;
• a second step of supplying the second process gas from the second gas source through the second gas introducing pipe to and through the gas supply means onto the substrate to reduce the first process gas supplied to the substrate, thereby forming a film on the substrate;
• a third step of purging the processing vessel by evacuating the processing vessel while supplying the inert gas from the third gas source into the processing vessel through said at least one of the first and second gas introducing pipes and the gas supply means,
• wherein the first and second steps are repeated with the third step of purging being carried out between each of the first and second steps and between the second step and the first step of each repetition of the first and second steps so that the third step reduces residual gas in the processing vessel, including residual gas absorbed on an inner wall of the processing vessel, due to the previous performance of the first or second steps to a level of 1 to 30% based on the entire capacity of the processing vessel.

A method of forming a film with ALD using a chemical vapor deposition apparatus comprising (i) a processing vessel, (ii) a mounting member which is provided in the processing vessel and supports a substrate thereon, (iii) heating means which heat the substrate supported by the mounting member, (iv) gas supply means having a plurality of gas spray ports for spraying gas onto the substrate in the process vessel, (v) evacuating means for evacuating the gas in the processing vessel so that the gas sprayed onto the substrate flows downwardly, (vi) a first gas source for storing a first process gas, (vii) a second gas source for storing a second process gas, (viii) a third gas source for storing an inert gas, (ix) a first gas introducing pipe which connects the first gas source to the gas supply means, and (x) a second gas introducing pipe which connects the second gas source to the gas supply means, at least one of the first and second gas introducing gas pipes connecting the third gas source to the gas supply means,

• the method comprising of:
• a first step of supplying the first process gas from the first gas source through the first gas introducing pipe to and through the gas supply means onto the substrate within the processing vessel;
• a second step of supplying the second process gas from the second gas source through the second gas introducing pipe to and through the gas supply means onto the substrate to reduce the first process gas supplied to the substrate, thereby forming a film containing refractory metal on the substrate;
• a third step of purging the processing vessel by evacuating the processing vessel while supplying the inert gas from the third gas source into the processing vessel through said at least one of the first and second gas introducing pipes and the gas supply means,
• wherein the first and second steps are repeated with the third step of purging being carried out between each of the first and second steps and between the second step and the first step of each repetition of the first and second steps, with the third step being carried out by evacuating the processing vessel to a vacuum degree of 0.1 Torr so as to reduce a total quantity of residual gas in the processing vessel, including residual gas absorbed on an inner wall of the processing vessel, due to the previous performance of the first or second steps to a level of 1 to 30% based on the entire capacity of the processing vessel.

A method of forming a film with ALD using a chemical vapor deposition apparatus comprising (i) a processing vessel, (ii) a mounting member which is provided in the processing vessel and supports a substrate thereon, (iii) heating means which heat the substrate supported by the mounting member, (iv) gas supply means having a plurality of gas spray ports for spraying gas onto the substrate in the process vessel, (v) evacuating means for evacuating the gas in the processing vessel so that the gas sprayed onto the substrate flows downwardly, (vi) a first gas source for storing a first process gas including refractory metallic atoms, (vii) a second gas source for storing a second process gas including a reducing gas, (viii) a third gas source for storing an inert gas, (ix) a first gas introducing pipe which connects the first gas source to the gas supply means, and (x) a second gas introducing pipe which connects the second gas source to the gas supply means, at least one of the first and second gas introducing pipes connecting the third gas source to the gas supply means,

• the method comprising of:
• a first step of supplying the first process gas from the first gas source onto the substrate within the processing vessel, through the first gas introducing pipe and the gas supply means;
• a second step of supplying the second process gas from the second gas source onto the substrate to reduce the first process gas supplied to the substrate, through the second gas introducing pipe and the gas supply means, thereby forming a film of refractory metal on the substrate;
• and
• a step of purging the processing vessel by evacuating the processing vessel while supplying the inert gas into the processing vessel from the third gas source, through said at least one of the first and second introducing pipes and the gas supply means,
• the first and second steps being repeately several times, and the purging step being carried out between the first and second steps, and the purging step reducing the residual gas which has been supplied in the processing vessel by the previous step of first and second steps to a level of 1 to 30% based on the entire capacity of the processing vessel.