Method for forming low-k hard film

A method for forming a hard film on an insulation film formed on a semiconductor substrate by plasma reaction, comprising the steps of:

• forming an insulation film on a semiconductor substrate placed in a reaction space by plasma polymerization using a silicon-containing hydrocarbon compound;
• vaporizing a silicon-containing hydrocarbon compound to provide a source gas, said silicon-containing hydrocarbon compound comprising a cyclic Si-containing hydrocarbon compound and/or a linear Si-containing hydrocarbon compound, as a basal structure, with reactive groups for forming oligomers using the basal structure;
• introducing a reaction gas comprising the source gas and a carrier gas into the reaction space;
• and
• forming a hard film on the insulation film by activating plasma polymerization reaction using a combination of low-frequency RF power and high-frequency RF power in the reaction space, wherein the plasma polymerization reaction is activated while controlling the flow of the reaction gas to lengthen a residence time, Rt, of the reaction gas in the reaction space, wherein 100 msec≦Rt,
• Rt[s]=9.42×107(Pr·Ts/Ps·Tr)rw2d/F
• wherein:
• Pr:
• reaction space pressure (Pa)
• Ps:
• standard atmospheric pressure (Pa)
• Tr:
• average temperature of the reaction (K)
• Ts:
• standard temperature (K)
• rw:
• radius of the silicon substrate (m)
• d:
• space between the silicon substrate and the upper electrode (m)
• F:
• total flow volume of the reaction gas (sccm).

A method for forming a hard film on an insulation film formed on a semiconductor substrate by plasma reaction, comprising the steps of:

• vaporizing a silicon-containing hydrocarbon compound to provide a source gas, said silicon-containing hydrocarbon compound comprising a cyclic Si-containing hydrocarbon compound and/or a linear Si-containing hydrocarbon compound, as a basal structure, with reactive groups for forming oligomers using the basal structure;
• introducing a reaction gas comprising the source gas and an additive gas into a reaction space for plasma CVD processing wherein a semiconductor substrate on which an insulation film is formed is placed, said additive gas being selected from the group consisting of C1-6 saturated or unsaturated hydrocarbon, C1-6 alkanol, and C3-20 ether;
• and
• forming a hard film on the insulation film by activating plasma polymerization reaction using radio-frequency RF power in the reaction space, wherein the plasma polymerization reaction is activated while controlling the flow of the reaction gas to lengthen a residence time, Rt, of the reaction gas in the reaction space, wherein 100 msec ≦Rt,
• Rt[s]=9.42×107(Pr·Ts/Ps·Tr)rw2d/F
• wherein:
• Pr:
• reaction space pressure (Pa)
• Ps:
• standard atmospheric pressure (Pa)
• Tr:
• average temperature of the reaction (K)
• Ts:
• standard temperature (K)
• rw:
• radius of the silicon substrate (m)
• d:
• space between the silicon substrate and the upper electrode (m)
• F:
• total flow volume of the reaction gas (sccm).

A method for forming a hard film on an insulation film formed on a semiconductor substrate by plasma reaction, comprising the steps of:

• vaporizing a silicon-containing hydrocarbon compound to provide a source gas, said silicon-containing hydrocarbon compound comprising a cyclic Si-containing hydrocarbon compound and/or a linear Si-containing hydrocarbon compound, as a basal structure, with reactive groups for forming oligomers using the basal structure;
• introducing a reaction gas comprising the source gas into a reaction space for plasma CVD processing wherein a semiconductor substrate on which an insulation film is formed is placed;
• and
• forming a hard film on the insulation film by activating plasma polymerization reaction using radio-frequency RF power in the reaction space, wherein the plasma polymerization reaction is activated while controlling the flow of the reaction gas to lengthen a residence time, Rt, of the reaction gas in the reaction space, wherein 100 msec ≦Rt,
• Rt[s]=9.42×107(Pr·Ts/Ps·Tr)rw2d/F
• wherein:
• Pr:
• reaction space pressure (Pa)
• Ps:
• standard atmospheric pressure (Pa)
• Tr:
• average temperature of the reaction (K)
• Ts:
• standard temperature (K)
• rw:
• radius of the silicon substrate (m)
• d:
• space between the silicon substrate and the upper electrode (m)
• F:
• total flow volume of the reaction gas (sccm).