Selective deposition of metal-containing cap layers for semiconductor devices

A method of forming a semiconductor device, comprising:

• providing a patterned substrate containing a dielectric layer having first dielectric layer surfaces, the patterned substrate further containing metal surfaces inside recessed features in the dielectric layer;
• modifying the first dielectric layer surfaces by exposure to a first silicon-containing reactant gas containing a hydrophobic functional group, the modifying substituting a hydrophilic functional group in the first dielectric layer surfaces with the hydrophobic functional group;
• and
• depositing first Ru metal cap layers selectively on the metal surfaces by exposing the modified first dielectric layer surfaces and the metal surfaces to a first deposition gas containing Ru3(CO)12-precursor vapor and CO carrier gas.

A method of forming a semiconductor device, comprising:

• providing a substrate containing copper (Cu) metal surfaces and dielectric layer surfaces, wherein the Cu metal surfaces are located on planarized Cu metal layers filling recessed features in a dielectric layer;
• modifying the dielectric layer surfaces by exposure to a silicon-containing reactant gas containing a hydrophobic functional group, the modifying substituting a hydrophilic functional group in the dielectric layer surfaces with the hydrophilic functional group;
• and
• depositing Ru metal cap layers selectively on the Cu metal surfaces by exposing the modified dielectric layer surfaces and the Cu metal surfaces to a deposition gas containing Ru3(CO)12 precursor vapor and CO carrier gas.