Techniques herein provide methods for depositing spin-on metal materials for creating metal hard mask (MHM) structures without voids in the deposition. This includes effective spin-on deposition of TiOx, ZrOx, SnOx, HFOx, TaOx, et cetera. Such materials can help to provide differentiation of material etch resistivity for differentiation. By enabling spin-on metal hard mask (MHM) for use with a multi-line layer, a slit-based or self-aligned blocking strategy can be effectively used. Techniques herein include identifying a fill material to fill particular openings in a given relief pattern, modifying a surface energy value of surfaces within the opening such that a contact angle value of an interface between the fill material in liquid form and the sidewall or floor surfaces enables gap-free or void-free filling.

Methods for pre-cleaning substrates having metal and dielectric surfaces are described. The substrate is exposed to a strong reductant to remove contaminants from the metal surface and damage the dielectric surface. The substrate is then exposed to an oxidation process to repair the damage to the dielectric surface and oxidize the metal surface. The substrate is then exposed to a weak reductant to reduce the metal oxide to a pure metal surface without substantially affecting the dielectric surface. Processing tools and computer readable media for practicing the method are also described.

In some aspects, methods of forming a metal sulfide thin film are provided. According to some methods, a metal sulfide thin film is deposited on a substrate in a reaction space in a cyclical process where at least one cycle includes alternately and sequentially contacting the substrate with a first vapor-phase metal reactant and a second vapor-phase sulfur reactant. In some aspects, methods of forming a three-dimensional architecture on a substrate surface are provided. In some embodiments, the method includes forming a metal sulfide thin film on the substrate surface and forming a capping layer over the metal sulfide thin film. The substrate surface may comprise a high-mobility channel.

A method of fabricating a semiconductor structure includes: forming a conductive layer on a first insulating layer; etching a portion of the conductive layer to expose a portion of the first insulating layer; deforming a surface of the portion of the first insulating layer to form a rough surface of the first insulating layer; and removing a residue of the conductive layer on the rough surface of the first insulating layer.

A method for selectively modifying a base material surface, includes applying a composition on a surface of a base material to form a coating film. The coating film is heated. The base material includes a surface layer which includes a first region including silicon. The composition includes a first polymer and a solvent. The first polymer includes at an end of a main chain or a side chain thereof, a group including a first functional group capable of forming a bond with the silicon. The first region preferably contains a silicon oxide, a silicon nitride, or a silicon oxynitride. The base material preferably further includes a second region that is other than the first region and that contains a metal; and the method preferably further includes, after the heating, removing with a rinse agent a portion formed on the second region, of the coating film.

A method for forming a silicon dioxide film and a method for forming a metal gate are provided. The method for forming a silicon dioxide film includes: forming a silicon dioxide layer on a semiconductor substrate, performing a nitrogen treatment to the silicon dioxide layer to convert the silicon dioxide layer of partial thickness into a mixed layer of silicon nitride and silicon oxynitride; and removing the mixed layer to form a silicon dioxide film on the semiconductor substrate.

There is provided a technique which includes: forming a first film containing silicon, oxygen, carbon and nitrogen on a substrate by performing a first cycle a predetermined number of times, the first cycle including non-simultaneously performing: forming a first layer containing silicon, oxygen, carbon and nitrogen by simultaneously supplying first aminosilane and an oxidant to the substrate; and performing a first modifying process to the first layer under a first temperature; and performing a second modifying process to the first film under a second temperature that is higher than the first temperature.

Methods of depositing a film selectively onto a first material relative to a second material are described. The substrate is pre-cleaned by heating the substrate to a first temperature, cleaning contaminants from the substrate and activating the first surface to promote formation of a self-assembled monolayer (SAM) on the first material. A SAM is formed on the first material by repeated cycles of SAM molecule exposure, heating and reactivation of the first material. A final exposure to the SAM molecules is performed prior to selectively depositing a film on the second material. Apparatus to perform the selective deposition are also described.

A pattern-forming method includes applying a first composition on a surface layer of a substrate to form a first coating film. The surface layer includes a first region which includes a metal atom, and a second region which includes a silicon atom. The first coating film is heated. A portion other than a portion formed on the first region or a portion other than a portion formed on the second region of the first coating film heated is removed, thereby forming a first lamination portion. A second composition is applied on the substrate on which the first lamination portion is formed to form a second coating film. The second coating film is heated or exposed. A portion other than a portion formed on the first lamination portion of the second coating film heated or exposed is removed, thereby forming a second lamination portion.

A substrate processing apparatus configured to process a combined substrate in which a first substrate having thereon a device layer and a second substrate are bonded to each other includes a holder configured to hold a rear surface of the second substrate; a processing unit configured to process the first substrate held by the holder; a first processing liquid supply configured to etch a front surface of the first substrate by supplying a first processing liquid to the front surface of the first substrate opposite to a surface thereof where the device layer is provided; and a second processing liquid supply configured to remove a metal contaminant on the rear surface of the second substrate by supplying a second processing liquid to the rear surface of the second substrate.