Methods of selectively depositing a low-k dielectric film are described. In one or more embodiments, the methods include exposing a substrate to a blocking compound, the substrate including a first surface and a second surface, the first surface including hydrogen-terminated silicon, the blocking compound selectively depositing on the first surface to form a blocked first surface; and selectively depositing the low-k dielectric film on the second surface. Methods of forming an inner spacer layer are described. In one or more embodiments, the methods include pretreating a substrate to remove oxide from a hydrogen-terminated silicon (Si) channel of the substrate, the substrate including the hydrogen-terminated silicon channel and a silicon germanium (SiGe) surface; exposing the substrate to a blocking compound, the blocking compound selectively depositing on the hydrogen-terminated silicon (Si) channel to form a blocked silicon channel; and depositing the inner spacer layer selectively on the silicon germanium surface.

Methods for filling a recessed feature on a substrate are disclosed. The methods disclosed include depositing a flowable layer structure on the substrate and heating the flowable layer structure above the glass transition temperature of the flowable layer structure. Methods for depositing the flowable layer structure include depositing an aluminum oxide based flowable layer structure employing atomic layer deposition processes.

In some embodiments, methods are provided for simultaneously and selectively depositing a first material on a first surface of a substrate and a second, different material on a second, different surface of the same substrate using the same reaction chemistries. For example, a first material may be selectively deposited on a metal surface while a second material is simultaneously and selectively deposited on an adjacent dielectric surface. The first material and the second material have different material properties, such as different etch rates.