A method performed by a film deposition apparatus includes supplying a first reaction gas, which is adsorbable to hydroxyl groups, to a surface of a substrate and causing the first reaction gas to be adsorbed onto the surface of the substrate; supplying a second reaction gas to the substrate and causing the second reaction gas to react with the first reaction gas adsorbed onto the surface of the substrate to form a reaction product on the substrate; supplying an activated third reaction gas to the substrate to modify a surface of the reaction product; and supplying a fourth reaction gas including a hydrogen-containing gas to at least a partial area of the modified surface of the reaction product to form hydroxyl groups on at least the partial area.

A film deposition device includes a reaction gas supply part which is in communication with a process space defined between a placement part and a ceiling part. An annular gap in a plan view exists between an outer peripheral portion of the placement part and an outer peripheral portion of the ceiling part in circumferential directions of the placement part and the ceiling part. A reaction gas supplied from the reaction gas supply part into the process space via the ceiling part flows outside of the process space via the annular gap. A plurality of gas flow channels, which is used for forming gas-flow walls, is formed in the outer peripheral portion of the ceiling part which provides the annular gap.

Provided herein are methods and apparatus for filling one or more gaps on a semiconductor substrate. The disclosed embodiments are especially useful for forming seam-free, void-free fill in both narrow and wide features. The methods may be performed without any intervening etching operations to achieve a single step deposition. In various implementations, a first operation is performed using a novel PEALD fill mechanism to fill narrow gaps and line wide gaps. A second operation may be performed using PECVD methods to continue filling the wide gaps.

Provided herein are methods and apparatus for filling one or more gaps on a semiconductor substrate. The disclosed embodiments are especially useful for forming seam-free, void-free fill in both narrow and wide features. The methods may be performed without any intervening etching operations to achieve a single step deposition. In various implementations, a first operation is performed using a novel PEALD fill mechanism to fill narrow gaps and line wide gaps. A second operation may be performed using PECVD methods to continue filling the wide gaps.

A method of depositing silicon nitride films on semiconductor substrates processed in a micro-volume of a plasma enhanced atomic layer deposition (PEALD) reaction chamber wherein a single semiconductor substrate is supported on a ceramic surface of a pedestal and process gas is introduced through gas outlets in a ceramic surface of a showerhead into a reaction zone above the semiconductor substrate, includes (a) cleaning the ceramic surfaces of the pedestal and showerhead with a fluorine plasma, (b) depositing a halide-free atomic layer deposition (ALD) oxide undercoating on the ceramic surfaces, (c) depositing a precoating of ALD silicon nitride on the halide-free ALD oxide undercoating, and (d) processing a batch of semiconductor substrates by transferring each semiconductor substrate into the reaction chamber and depositing a film of ALD silicon nitride on the semiconductor substrate supported on the ceramic surface of the pedestal.

Methods and apparatus to form films on sensitive substrates while preventing damage to the sensitive substrate are provided herein. In certain embodiments, methods involve forming a bilayer film on a sensitive substrate that both protects the underlying substrate from damage and possesses desired electrical properties. Also provided are methods and apparatus for evaluating and optimizing the films, including methods to evaluate the amount of substrate damage resulting from a particular deposition process and methods to determine the minimum thickness of a protective layer. The methods and apparatus described herein may be used to deposit films on a variety of sensitive materials such as silicon, cobalt, germanium-antimony-tellerium, silicon-germanium, silicon nitride, silicon carbide, tungsten, titanium, tantalum, chromium, nickel, palladium, ruthenium, or silicon oxide.

A method for processing a substrate in a substrate processing system includes flowing reactant gases into a process chamber including a substrate, supplying a first power level sufficient to promote rearrangement of molecules on a surface of the substrate, waiting a first predetermined period, and, after the first predetermined period, performing plasma-enhanced, pulsed chemical vapor deposition of film on the substrate by supplying one or more precursors while supplying a second power level for a second predetermined period. The second power level is greater than the first power level. The method further includes removing reactants from the process chamber.

An oxide or nitride film containing carbon and at least one of silicon and metal is formed by ALD conducting one or more process cycles, each process cycle including: feeding a first precursor in a pulse to adsorb the first precursor on a substrate; feeding a second precursor in a pulse to adsorb the second precursor on the substrate; and forming a monolayer constituting an oxide or nitride film containing carbon and at least one of silicon and metal on the substrate by undergoing ligand substitution reaction between first and second functional groups included in the first and second precursors adsorbed on the substrate. The ligand may be a halogen group, —NR.sub.2, or —OR.

A method of forming a silicon nitride film on a substrate in a vacuum vessel, includes forming the silicon nitride film by depositing a layer of reaction product by repeating a cycle a plurality of times. The cycle includes a first process of supplying a gas of a silicon raw material to the substrate to adsorb the silicon raw material to the substrate, subsequently, a second process of supplying a gas of ammonia in a non-plasma state to the substrate to physically adsorb the gas of the ammonia to the substrate, and subsequently, a third process of supplying active species obtained by converting a plasma forming gas containing a hydrogen gas for forming plasma into plasma to the substrate and causing the ammonia physically adsorbed to the substrate to react with the silicon raw material to form the layer of reaction product.

A semiconductor device manufacturing method includes: a primary process of supplying a process gas to a substrate having a depression formed therein to form a third layer and filling the depression with the third layer, the substrate including a first layer whose surface is exposed as an upper surface of the substrate and a second layer formed in at least a sidewall of the depression having the sidewall and a floor surface; performing an etching process of etching the third layer to expose the upper surface, and halting the etching of the third layer while remaining the third layer formed within the depression; and performing a secondary process of supplying the process gas to the substrate to form the third layer so that the depression is filled with the third layer with no clearance.