Abstract: A method for processing a substrate includes treating the substrate with a small molecular inhibitor (SMI), the substrate including a recess formed in a dielectric layer and a first metal layer in the recess, the SMI covering a surface of the first metal layer. The method further includes, after treating the substrate with the SMI, treating the substrate with a large molecular inhibitor (LMI), the LMI covering sidewalls of the dielectric layer in the recess. The method further includes heating the substrate to remove the SMI from the first metal layer and to expose the first metal layer in the recess, where the LMI remains on the sidewalls after removing the SMI from the first metal layer. The method further includes depositing a second metal over the first metal layer in the recess, where the LMI covering the sidewalls prevents deposition of the second metal on the dielectric layer.

Abstract: Embodiments of methods are provided for thermal dry etching of a ruthenium (Ru) metal layer. In the disclosed embodiments, a substrate containing a Ru metal layer formed thereon is exposed to a gas pulse sequence, while the substrate is held at a relatively high substrate temperature (e.g., a temperature greater than or equal to about 160° C.), to provide thermal etching of the Ru metal layer. As described further herein, the gas pulse sequence may generally include a plurality of gas pulses, which are supplied to the substrate sequentially with substantially no overlap between gas pulses. The gas pulses supplied to the substrate form: (i) volatile reaction products that are vaporized from the Ru surface, and (ii) non-volatile oxide surface layers that are removed from the Ru surface by the next gas pulse, resulting in atomic layer etching (ALE) of the Ru metal layer.

Abstract: A method for filling recessed features with a low-resistivity metal. The method includes providing a patterned substrate containing a recessed feature formed in a first layer and a second layer that is exposed in the recessed feature, forming a nucleation enhancement layer on a sidewall of the first layer in the recessed feature and depositing a metal layer in the recessed feature by vapor phase deposition, where the metal layer is deposited on the second layer and on the nucleation enhancement layer. An initial metal layer may be selectively formed on the second layer in the recessed feature before forming the nucleation enhancement layer.

Abstract: Embodiments of methods are provided for thermal dry etching of a ruthenium (Ru) metal layer. In the disclosed embodiments, a substrate containing a Ru metal layer formed thereon is exposed to a gas pulse sequence, while the substrate is held at a relatively high substrate temperature (e.g., a temperature greater than or equal to about 160° C.), to provide thermal etching of the Ru metal layer. As described further herein, the gas pulse sequence may generally include a plurality of gas pulses, which are supplied to the substrate sequentially with substantially no overlap between gas pulses. The gas pulses supplied to the substrate form: (i) volatile reaction products that are vaporized from the Ru surface, and (ii) non-volatile oxide surface layers that are removed from the Ru surface by the next gas pulse, resulting in atomic layer etching (ALE) of the Ru metal layer.

Abstract: A method for processing a substrate includes treating the substrate with a small molecular inhibitor (SMI), the substrate including a recess formed in a dielectric layer and a first metal layer in the recess, the SMI covering a surface of the first metal layer. The method further includes, after treating the substrate with the SMI, treating the substrate with a large molecular inhibitor (LMI), the LMI covering sidewalls of the dielectric layer in the recess. The method further includes heating the substrate to remove the SMI from the first metal layer and to expose the first metal layer in the recess, where the LMI remains on the sidewalls after removing the SMI from the first metal layer. The method further includes depositing a second metal over the first metal layer in the recess, where the LMI covering the sidewalls prevents deposition of the second metal on the dielectric layer.

Abstract: A method of controlling the forming voltage of a dielectric film in a resistive random access memory (ReRAM) device. The method includes depositing a dielectric film contains intrinsic defects on a substrate, forming a plasma-excited treatment gas containing H2 gas, and exposing the dielectric film to the plasma-excited treatment gas to create additional defects in the dielectric film without substantially changing a physical thickness of the dielectric film, where the additional defects lower the forming voltage needed for generating an electrically conducting filament across the dielectric film. The dielectric film can include a metal oxide film and the plasma-excited treatment gas may be formed using a microwave plasma source.

Abstract: A method for filling recessed features with a low-resistivity metal. The method includes providing a patterned substrate containing a recessed feature formed in a first layer and a second layer that is exposed in the recessed feature, and pre-treating the substrate with a surface modifier that increases metal deposition selectivity on the second layer relative to on the first layer, depositing a metal layer on the substrate by vapor phase deposition, where the metal layer is preferentially deposited on the second layer in the recessed feature, and removing metal nuclei deposited on the first layer, including on a field area and on sidewalls of the first layer in the recessed feature, to selectively form the metal layer on the second layer in the recessed feature. The steps of pre-treating, depositing and removing may be repeated at least once to increase a thickness of the metal layer in the recessed feature.

Abstract: A method for filling recessed features with a low-resistivity metal. The method includes providing a patterned substrate containing a recessed feature formed in a first layer and a second layer that is exposed in the recessed feature, forming a nucleation enhancement layer on a sidewall of the first layer in the recessed feature and depositing a metal layer in the recessed feature by vapor phase deposition, where the metal layer is deposited on the second layer and on the nucleation enhancement layer. An initial metal layer may be selectively formed on the second layer in the recessed feature before forming the nucleation enhancement layer.

Abstract: A method for filling recessed features with a low-resistivity metal includes providing a patterned substrate containing a recessed feature formed in a first layer and a second layer that is exposed in the recessed feature, pre-treating the substrate with a surface modifier that increases metal deposition selectivity on the second layer relative to on the first layer, and depositing a metal layer on the substrate by vapor phase deposition, where the metal layer is preferentially deposited on the second layer in the recessed feature. The method further includes removing metal nuclei deposited on the first layer, including on a field area and on sidewalls of the first layer in the recessed feature, to selectively form the metal layer on the second layer in the recessed feature, where the removing includes exposing the patterned substrate to an etching gas containing ozone.

Abstract: A method for filling recessed features with a low-resistivity metal. The method includes providing a patterned substrate containing a recessed feature formed in a first layer and a second layer that is exposed in the recessed feature, and pre-treating the substrate with a surface modifier that increases metal deposition selectivity on the second layer relative to on the first layer, depositing a metal layer on the substrate by vapor phase deposition, where the metal layer is preferentially deposited on the second layer in the recessed feature, and removing metal nuclei deposited on the first layer, including on a field area and on sidewalls of the first layer in the recessed feature, to selectively form the metal layer on the second layer in the recessed feature. The steps of pre-treating, depositing and removing may be repeated at least once to increase a thickness of the metal layer in the recessed feature.

Abstract: A method of controlling the forming voltage of a dielectric film in a resistive random access memory (ReRAM) device. The method includes depositing a dielectric film contains intrinsic defects on a substrate, forming a plasma-excited treatment gas containing H2 gas, and exposing the dielectric film to the plasma-excited treatment gas to create additional defects in the dielectric film without substantially changing a physical thickness of the dielectric film, where the additional defects lower the forming voltage needed for generating an electrically conducting filament across the dielectric film. The dielectric film can include a metal oxide film and the plasma-excited treatment gas may be formed using a microwave plasma source.

Abstract: A method for filling recessed features with a low-resistivity metal. The method includes providing a patterned substrate containing a recessed feature formed in a first layer and a second layer that is exposed in the recessed feature, and pre-treating the substrate with a surface modifier that increases metal deposition selectivity on the second layer relative to on the first layer, depositing a metal layer on the substrate by vapor phase deposition, where the metal layer is preferentially deposited on the second layer in the recessed feature, and removing metal nuclei deposited on the first layer, including on a field area and on sidewalls of the first layer in the recessed feature, to selectively form the metal layer on the second layer in the recessed feature. The steps of pre-treating, depositing and removing may be repeated at least once to increase a thickness of the metal layer in the recessed feature.

Abstract: A method of controlling the forming voltage of a dielectric film in a resistive random access memory (ReRAM) device. The method includes depositing a dielectric film contains intrinsic defects on a substrate, forming a plasma-excited treatment gas containing H2 gas, and exposing the dielectric film to the plasma-excited treatment gas to create additional defects in the dielectric film without substantially changing a physical thickness of the dielectric film, where the additional defects lower the forming voltage needed for generating an electrically conducting filament across the dielectric film. The dielectric film can include a metal oxide film and the plasma-excited treatment gas may be formed using a microwave plasma source.

Abstract: A process is provided in which etched layer(s) are protected from residues or defects caused by or resulting from exposure to atmospheric conditions. Protection is provided through the formation of an encapsulation layer post etch. In one embodiment, the encapsulation is provided by a thin layer formed in an atomic layer deposition (ALD) process. The thin layer prevents the etched layer(s) from exposure to air. This encapsulation process may take place after the etch process thus allowing for substrates to be subsequently exposed to atmospheric conditions with little or no queue time constraints being needed for staging subsequent wet clean processing steps. In one embodiment, the encapsulation process may be performed with no vacuum break between the etch process and the encapsulation process. In one embodiment, the encapsulation film is compatible with subsequent wet process steps and can be removed during this wet process steps without adverse effects.

Abstract: A method of controlling the forming voltage of a dielectric film in a resistive random access memory (ReRAM) device. The method includes depositing a dielectric film contains intrinsic defects on a substrate, forming a plasma-excited treatment gas containing H2 gas, and exposing the dielectric film to the plasma-excited treatment gas to create additional defects in the dielectric film without substantially changing a physical thickness of the dielectric film, where the additional defects lower the forming voltage needed for generating an electrically conducting filament across the dielectric film. The dielectric film can include a metal oxide film and the plasma-excited treatment gas may be formed using a microwave plasma source.

Abstract: A method is provided for void-free Ru metal filling of features in a substrate. The method includes providing a substrate containing features, depositing a Ru metal layer in the features, removing the Ru metal layer from a field area around an opening of the features, and depositing additional Ru metal in the features, where the additional Ru metal is deposited in the features at a higher rate than on the field area. According to one embodiment, the additional Ru metal is deposited until the features are fully filled with Ru metal.

Abstract: A method for filling recessed features with a low-resistivity metal. The method includes providing a patterned substrate containing a recessed feature formed in a first layer and a second layer that is exposed in the recessed feature, and pre-treating the substrate with a surface modifier that increases metal deposition selectivity on the second layer relative to on the first layer, depositing a metal layer on the substrate by vapor phase deposition, where the metal layer is preferentially deposited on the second layer in the recessed feature, and removing metal nuclei deposited on the first layer, including on a field area and on sidewalls of the first layer in the recessed feature, to selectively form the metal layer on the second layer in the recessed feature. The steps of pre-treating, depositing and removing may be repeated at least once to increase a thickness of the metal layer in the recessed feature.

Abstract: A process is provided in which etched layer(s) are protected from residues or defects caused by or resulting from exposure to atmospheric conditions. Protection is provided through the formation of an encapsulation layer post etch. In one embodiment, the encapsulation is provided by a thin layer formed in an atomic layer deposition (ALD) process. The thin layer prevents the etched layer(s) from exposure to air. This encapsulation process may take place after the etch process thus allowing for substrates to be subsequently exposed to atmospheric conditions with little or no queue time constraints being needed for staging subsequent wet clean processing steps. In one embodiment, the encapsulation process may be performed with no vacuum break between the etch process and the encapsulation process. In one embodiment, the encapsulation film is compatible with subsequent wet process steps and can be removed during this wet process steps without adverse effects.

Abstract: A method is provided for void-free Ru metal filling of features in a substrate. The method includes providing a substrate containing features, depositing a Ru metal layer in the features, removing the Ru metal layer from a field area around an opening of the features, and depositing additional Ru metal in the features, where the additional Ru metal is deposited in the features at a higher rate than on the field area. According to one embodiment, the additional Ru metal is deposited until the features are fully filled with Ru metal.

Abstract: Methods for integration of conformal barrier layers and Ru metal liners with Cu metallization in semiconductor manufacturing are described in several embodiments. According to one embodiment, the method includes providing a substrate containing a recessed feature, depositing a barrier layer in the recessed feature, depositing a Ru metal liner on the barrier layer, and exposing the substrate to an oxidation source gas to oxidize the barrier layer through the Ru metal liner. The method further includes filling the recessed feature with CuMn metal using an ionized physical vapor deposition (IPVD) process, heat-treating the substrate to diffuse Mn from the CuMn metal to the oxidized barrier layer, and reacting the diffused Mn with the oxidized barrier layer to form a Mn-containing diffusion barrier.