Substrate processing method and substrate processing apparatus

Abstract

A substrate processing method for removing a copper oxide film on a surface of Cu and a Cu-containing residue adhered to an interlayer insulating film in a Cu wiring structure on a substrate by using an organic acid-containing gas is provided. The substrate processing method includes removing the Cu-containing residue by etching by supplying the substrate with a processing gas containing an organic acid gas, after the temperature of the substrate is set to be maintained at a first temperature; and removing the copper oxide film on the surface of Cu by means of a reduction reaction by supplying the substrate with the processing gas containing the organic acid gas, after the temperature of the substrate is set to be maintained at a second temperature that is higher than the first temperature.

1 . A substrate processing method for removing a copper oxide film on a surface of Cu and a Cu-containing residue adhered to an interlayer insulating film in a Cu wiring structure on a substrate by using an organic acid-containing gas, the substrate processing method comprising:
 removing the Cu-containing residue by etching by supplying the substrate with a processing gas containing an organic acid gas, after the temperature of the substrate is set to be maintained at a first temperature; and   removing the copper oxide film on the surface of Cu by means of a reduction reaction by supplying the substrate with the processing gas containing the organic acid gas, after the temperature of the substrate is set to be maintained at a second temperature that is higher than the first temperature.   
     
     
         2 . The substrate processing method of  claim 1 , wherein the interlayer insulating film is a low-k film. 
     
     
         3 . The substrate processing method of  claim 1 , wherein the organic acid is a carboxylic acid. 
     
     
         4 . The substrate processing method of  claim 1 , wherein the carboxylic acid is a formic acid. 
     
     
         5 . The substrate processing method of  claim 3 , wherein the first temperature is within a range from about 100° C. to about 200° C., and the second temperature is within a range from about 200° C. to about 300° C. 
     
     
         6 . The substrate processing method of  claim 1 , wherein there is used a substrate processing apparatus including a chamber for accommodating a substrate, a mounting table for mounting thereon the substrate in the chamber, a heating mechanism for heating the substrate on the mounting table, a processing gas supply mechanism for supplying the processing gas containing an organic acid gas into the chamber, and a gas exhaust mechanism for exhausting the chamber,
 wherein the Cu-containing residue is removed by etching after the temperature of the substrate is set to be maintained at the first temperature by the heating mechanism and, then, the copper oxide film on the surface of Cu is removed after the temperature of the substrate is set to be maintained at the second temperature by the heating mechanism.   
     
     
         7 . The substrate processing method of  claim 1 , wherein there is used a substrate processing apparatus including a chamber for accommodating therein a substrate, a mounting table for mounting thereon the substrate in the chamber, a heating mechanism for heating the substrate on the mounting table, an energy medium gas supply mechanism for supplying a heated energy medium gas to the substrate on the mounting table, a processing gas supply mechanism for supplying the processing gas containing an organic acid gas into the chamber, and a gas exhaust mechanism for exhausting the chamber,
 wherein the Cu-containing residue is removed by etching after the temperature of the substrate is set to be maintained at the first temperature by the heating mechanism and, then, the copper oxide film on the surface of Cu is removed after the temperature of the substrate is set to be maintained at the second temperature by supplying the heated energy medium gas to the substrate on the mounting table from the energy medium gas supply mechanism.   
     
     
         8 . The substrate processing method of  claim 1 , wherein there is used a substrate processing apparatus including: a first processing unit, having a mounting table for mounting thereon a substrate and maintained at a temperature for heating the substrate mounted thereon to be maintained at the first temperature, for supplying the processing gas to the substrate on the mounting table; and a second processing unit, having a mounting table for mounting thereon the substrate and maintained at a temperature for heating the substrate mounted thereon to be maintained at the second temperature, for supplying the processing gas to the substrate on the mounting table,
 wherein the Cu-containing residue is removed by etching after the temperature of the substrate mounted on the mounting table of the first processing unit is set to be maintained at the first temperature and then, the copper oxide film on the surface of Cu is removed after the temperature of the substrate mounted on the mounting table of the second processing unit is set to be maintained at the second temperature.   
     
     
         9 . The substrate processing method of  claim 1 , wherein there is used a substrate processing apparatus including a processing chamber for processing therein a substrate, a substrate holding unit for holding a plurality of substrates in the processing chamber, a heating mechanism for heating the substrates in the processing chamber, a processing gas supply mechanism for supplying the processing gas containing an organic acid gas into the processing chamber, and a gas exhaust mechanism for exhausting the processing chamber,
 wherein the Cu-containing residue is removed by etching after the temperature of the substrate supported by the supporting unit in the processing chamber is set to be maintained at the first temperature by the heating mechanism and, then, the copper oxide film on the surface of Cu is removed after the temperature of the substrates is set to be maintained at the second temperature by the heating mechanism.   
     
     
         10 . A substrate processing apparatus for removing a copper oxide film on a surface of Cu and a Cu-containing residue adhered to an interlayer insulating film in a Cu wiring structure on a substrate by using an organic acid-containing gas, the substrate processing apparatus comprising:
 a chamber for accommodating a substrate;   a mounting table for mounting thereon the substrate in the chamber;   a heating mechanism for heating the substrate on the mounting table;   a processing gas supply mechanism for supplying a processing gas containing an organic acid gas into the chamber;   a gas exhaust mechanism for exhausting an interior of the chamber; and   a control mechanism for removing a Cu-containing residue by etching by supplying the substrate with the processing gas containing an organic acid gas after the temperature of the substrate mounted on the mounting table is set to be maintained at a first temperature by the heating mechanism, and then removing a copper oxide film on a surface of Cu by means of a reduction reaction by supplying the substrate with the processing gas containing an organic acid gas after the temperature of the substrate is set to be maintained at a second temperature higher than the first temperature by the heating mechanism.   
     
     
         11 . A substrate processing apparatus for removing a copper oxide film on a surface of Cu and a Cu-containing residue adhered to an interlayer insulating film in a Cu wiring structure on a substrate by using an organic acid-containing gas, the substrate processing apparatus comprising:
 a chamber for accommodating a substrate;   a mounting table for mounting thereon the substrate in the chamber;   a heating mechanism for heating the substrate on the mounting table;   an energy medium gas supply mechanism for supplying a heated energy medium gas to the substrate on the mounting table;   a processing gas supply mechanism for supplying a processing gas containing an organic acid gas into the chamber;   a gas exhaust mechanism for exhausting an interior of the chamber;   a control mechanism for removing a Cu-containing residue by etching by supplying the substrate with the processing gas containing an organic acid gas after the temperature of the substrate mounted on the mounting table is set to be maintained at a first temperature by the heating mechanism, and then removing a copper oxide film on a surface of Cu by means of a reduction reaction by supplying the substrate with the processing gas containing an organic acid gas after the temperature of the substrate is set to be maintained at a second temperature higher than the first temperature by supplying the heated energy medium gas to the substrate on the mounting table.   
     
     
         12 . A substrate processing apparatus for removing a copper oxide film on a surface of Cu and a Cu-containing residue adhered to an interlayer insulating film in a Cu wiring structure on a substrate by using a processing gas containing an organic acid, the substrate processing apparatus comprising:
 a first processing unit, having a mounting table maintained at a temperature for heating the substrate mounted thereon to be maintained at a first temperature, for supplying the processing gas onto the substrate on the mounting table;   a second processing unit, having a mounting table maintained at a temperature for heating the substrate mounted thereon to be maintained at a second temperature, for supplying the processing gas onto the substrate on the mounting table;   a transfer mechanism for transferring the substrate between the first processing unit and the second processing unit; and   a control mechanism for removing a Cu-containing residue by etching by supplying the substrate with the processing gas containing an organic acid gas after the temperature of the substrate mounted on the mounting table of the first processing unit is set to be maintained at the first temperature, and then removing a copper oxide film on a surface of Cu by means of a reduction reaction by supplying a processing gas containing an organic acid gas to the substrate by supplying the substrate with a processing gas containing an organic acid gas after the temperature of the substrate transferred on the mounting table of the second processing unit by the transfer mechanism is set to be maintained at the second temperature.   
     
     
         13 . A substrate processing apparatus for removing a copper oxide film on a surface of Cu and a Cu-containing residue adhered to an interlayer insulating film in a Cu wiring structure on a substrate by using an organic acid-containing gas, the substrate processing apparatus comprising:
 a processing chamber for processing a substrate;   a substrate supporting unit for supporting a plurality of substrates in the processing chamber;   a heating mechanism for heating the substrates in the processing chamber;   a processing gas supply mechanism for supplying a processing gas containing an organic acid gas into the processing chamber;   a control mechanism for removing a Cu-containing residue by etching by supplying the substrates with the processing gas containing an organic acid gas after the temperature of the substrates held by the substrate supporting unit in the processing chamber is set to be maintained at a first temperature by the heating mechanism, and then removing a copper oxide film on a surface of Cu by means of a reduction reaction by supplying the substrates with the processing gas containing an organic acid gas after the temperature of the substrates is set to be maintained at a second temperature higher than the first temperature by the heating mechanism.   
     
     
         14 . A non-transitory computer-readable storage medium storing a program for controlling a substrate processing apparatus, wherein the program, when executed by a computer, controls the substrate processing apparatus to perform the substrate processing method described in  claim 1 .