Surface Treatment For Selective Deposition

A reverse selective deposition method comprising:

• exposing a substrate to a surface pretreatment comprising ammonia, the substrate including at least one feature extending from a top surface of the substrate to a bottom, the at least one feature having a width between a first sidewall and a second sidewall, the bottom comprising a conductive material with a first surface and the first sidewall and second sidewall comprising an insulating material with a second surface, wherein the pretreatment chemisorbs nitrogen atoms to at least a portion of the first surface and forms a modified first surface;
• exposing the substrate to a blocking compound comprising a compound with a general formula R′═R″ or R′≡R″ to selectively form a blocking layer on the modified first surface, wherein the nitrogen atoms are interposed between at least some molecules of the blocking layer and the first surface;
• selectively depositing a barrier layer on the second surface over the blocking layer, the barrier layer selected from the group consisting of tantalum nitride and titanium nitride;
• and
• removing the blocking layer from the conductive material,
• wherein the surface pretreatment does not contain plasma and facilitates the removal of the blocking layer from the first surface.