Abstract: The present disclosure provides various embodiments of an improved wet atomic layer etching (ALE) process. More specifically, the present disclosure provides various embodiments of methods that improve a wet ALE process by providing a dynamic ALE cycle timing schedule that balances throughput and etch rate with post-etch surface roughness. As described in more detail below, the methods disclosed herein may adjust the purge timing between ALE cycles and/or between individual surface modification and selective dissolution steps to provide a desired throughput, etch rate and/or post-etch surface roughness in a wet ALE process.

Abstract: The present disclosure provides embodiments of processes and methods for stabilizing self-assembled monolayers (SAMs). In the present disclosure, a cyclic vapor deposition process is used to selectively deposit a polymer thin film on a SAM structure formed on a target material. The polymer thin film selectively deposited on the SAM structure stabilizes the SAM structure by: (a) healing defects in the SAM structure and providing blanket coverage over the target material surface, (b) preventing migration of SAM-forming molecules to neighboring non-target surfaces, and (c) increasing the thickness and rigidity of the SAM structure. In one embodiment, sequentially pulsed initiated chemical vapor deposition (spiCVD) is used to selectively deposit the polymer thin film on the SAM structure.

Abstract: The present disclosure provides a new wet atomic layer etch (ALE) process for etching copper. More specifically, the present disclosure provides various embodiments of methods that utilize new etch chemistries for etching copper in a wet ALE process. By utilizing the new etch chemistries disclosed herein within a wet ALE process, the present disclosure provides a highly selective etch of copper with monolayer precision.

Abstract: The present disclosure provides embodiments of improved area-selective deposition (ASD) processes and methods for selectively depositing polymer films on a variety of different target material. More specifically, the present disclosure provides improved ASD processes and related methods that use a cyclic vapor deposition process, which sequentially exposes a surface of a substrate to a polymer precursor followed by an initiator to selectively deposit a polymer thin film on a target material exposed on the substrate surface. The process of sequentially exposing the substrate surface to the precursor and the initiator can be repeated for one or more cycles of the cyclic vapor deposition process until a predetermined thickness of the polymer thin film is selectively deposited on the target material. In one embodiment, sequentially pulsed initiated chemical vapor deposition (spiCVD) is used to selectively deposit the polymer thin film on the target material.

Abstract: The present disclosure provides a new wet atomic layer etch (ALE) process for etching copper. More specifically, the present disclosure provides various embodiments of methods that utilize new etch chemistries for etching copper in a wet ALE process. By utilizing the new etch chemistries disclosed herein within a wet ALE process, the present disclosure provides a highly selective etch of copper with monolayer precision.

Abstract: A method for removal of stray Ru metal nuclei for selective Ru metal layer formation includes depositing ruthenium (Ru) metal on a patterned substrate by vapor phase deposition, where a Ru metal layer is deposited on a surface of a metal layer and Ru metal nuclei are deposited on a surface of a dielectric layer. The method further includes removing the Ru metal nuclei by gas phase etching using an ozone (O3) gas exposure that forms volatile ruthenium oxide species by oxidation of the Ru metal nuclei, and repeating the depositing and removing steps at least once to increase a thickness of the Ru metal layer, where the depositing is interrupted before the Ru metal nuclei reach a critical size that results in formation of non-volatile ruthenium oxide species and incomplete removal of the Ru metal nuclei during the gas phase etching.

Abstract: The present disclosure provides various embodiments of an improved wet atomic layer etching (ALE) process. More specifically, the present disclosure provides various embodiments of methods that improve a wet ALE process by providing a dynamic ALE cycle timing schedule that balances throughput and etch rate with post-etch surface roughness. As described in more detail below, the methods disclosed herein may adjust the purge timing between ALE cycles and/or between individual surface modification and selective dissolution steps to provide a desired throughput, etch rate and/or post-etch surface roughness in a wet ALE process.

Abstract: Provided is a pore-filling method for protecting the pores of a porous material. The method, which is performed using a modified i-CVD technique, involves filling the pores of a porous material with a gas phase monomer within a pressure chamber and subsequently polymerizing the monomer, both within the pores and on the surface of the material as an overburden. The method is solvent-free and can fill and protect pores of any size of any material.

Abstract: A method for processing a substrate that includes: loading the substrate in a plasma processing chamber; performing a cyclic plasma etch process including a plurality of cycles, where each cycle of the plurality of cycles includes: generating a first plasma from a first gas mixture including a fluorosilane and oxygen; performing a deposition step by exposing the substrate to the first plasma to form a passivation film including silicon and fluorine; generating a second plasma from a second gas mixture including a noble gas; and performing an etch step by exposing the substrate to the second plasma.

Abstract: The present disclosure provides a system for etching an exposed material on a substrate disposed within a process chamber using a hybrid atomic layer etching (ALE) process that combines a gas-phase surface modification step with a liquid-phase dissolution step within the same process chamber. In the hybrid ALE process disclosed herein, a gas-phase reactant is used to modify an exposed surface of the material to create a modified surface layer, and one or more liquid-phase reactants are used to selectively dissolve the modified surface layer without dissolving the material underlying the modified surface layer. Once the modified surface layer is selectively dissolved, the substrate may be dried and the gas-phase surface modification and liquid-phase dissolution steps may be repeated for one or more ALE cycles until a desired amount of the material is etched.

Abstract: The present disclosure provides a hybrid atomic layer etching (ALE) process that combines a gas-phase surface modification step with a liquid-phase dissolution step for etching an exposed material on a substrate disposed within a process chamber. In the hybrid ALE process disclosed herein, a gas-phase reactant is used to modify an exposed surface of the material to create a modified surface layer, and one or more liquid-phase reactants are used to selectively dissolve the modified surface layer without dissolving the material underlying the modified surface layer. Once the modified surface layer is selectively dissolved, the substrate may be dried and the gas-phase surface modification and liquid-phase dissolution steps may be repeated for one or more ALE cycles until a desired amount of the material is etched.

Abstract: An etching method includes: a physical adsorption process of physically adsorbing an adsorbate based on a first processing gas on a film to be etched under a condition that the pressure of the first processing gas is smaller than the saturated vapor pressure of the first processing gas with respect to a temperature of an object to be processed while cooling the object to be processed on which the film to be etched is formed; and an etching process of etching the film to be etched by reacting the adsorbate with the film to be etched by a plasma of a second processing gas.

Abstract: A plasma etching method includes a physisorption step for causing an adsorbate that is based on first processing gas to be physisorbed onto a film to be etched, while cooling an object to be processed on which the film to be etched is provided; and an etching step for etching the film to be etched by causing the adsorbate to react with the film to be etched, using the plasma of second processing gas.

Abstract: Method for selective etching of materials using an ultrathin etch stop layer (ESL), where the ESL is effective at a thickness as small as approximately one monolayer using atomic layer etching (ALE). A substrate processing method includes depositing a first film on a substrate, depositing a second film on the first film, and selectively etching the second film relative to the first film using an ALE process, where the etching self-terminates at an interface of the second film and the first film.

Abstract: Methods are disclosed that illuminate etch solutions to provide controlled etching of materials. An etch solution (e.g., gaseous, liquid, or combination thereof) with a first level of reactants is applied to the surface of a material to be etched. The etch solution is illuminated to cause the etch solution to have a second level of reactants that is greater than the first level. The surface of the material is modified (e.g., oxidized) with the illuminated etch solution, and the modified layer of material is removed. The exposing and removing can be repeated or cycled to etch the material. Further, for oxidation/dissolution embodiments the oxidation and dissolution can occur simultaneously, and the oxidation rate can be greater than the dissolution rate. The material can be a polycrystalline material, a polycrystalline metal, and/or other material. One etch solution can include hydrogen peroxide that is illuminated to form hydroxyl radicals.

Abstract: A plasma etching method includes a physisorption step for causing an adsorbate that is based on first processing gas to be physisorbed onto a film to be etched, while cooling an object to be processed on which the film to be etched is provided; and an etching step for etching the film to be etched by causing the adsorbate to react with the film to be etched, using the plasma of second processing gas.

Abstract: Provided is a pore-filling method for protecting the pores of a porous material. The method, which is performed using a modified i-CVD technique, involves filling the pores of a porous material with a gas phase monomer within a pressure chamber and subsequently polymerizing the monomer, both within the pores and on the surface of the material as an overburden. The method is solvent-free and can fill and protect pores of any size of any material.

Abstract: Methods and systems herein enable selective removal of ruthenium (Ru) metal at high throughput, and without potentially damaging effects of plasma. Techniques include a photo-assisted chemical vapor etch (PCVE) method to selectively remove Ru metal as a volatile species. A substrate with ruthenium surfaces is positioned within a processing chamber. A photo-oxidizer is received in vapor form in the processing chamber. The photo-oxidizer is a species that generates reactive oxygen species in response to actinic radiation. Reactive oxygen species are then generated by irradiation of the photo-oxidizer, such as with ultraviolet radiation. The reactive oxygen species react with ruthenium surfaces causing the ruthenium surfaces to become oxidized. Oxidized ruthenium is then removed from the substrate, such as be vaporization.

Abstract: Methods and systems herein enable selective removal of ruthenium (Ru) metal at high throughput, and without potentially damaging effects of plasma. Techniques include a photo-assisted chemical vapor etch (PCVE) method to selectively remove Ru metal as a volatile species. A substrate with ruthenium surfaces is positioned within a processing chamber. A photo-oxidizer is received in vapor form in the processing chamber. The photo-oxidizer is a species that generates reactive oxygen species in response to actinic radiation. Reactive oxygen species are then generated by irradiation of the photo-oxidizer, such as with ultraviolet radiation. The reactive oxygen species react with ruthenium surfaces causing the ruthenium surfaces to become oxidized. Oxidized ruthenium is then removed from the substrate, such as be vaporization.

Abstract: Methods are disclosed that illuminate etch solutions to provide controlled etching of materials. An etch solution (e.g., gaseous, liquid, or combination thereof) with a first level of reactants is applied to the surface of a material to be etched. The etch solution is illuminated to cause the etch solution to have a second level of reactants that is greater than the first level. The surface of the material is modified (e.g., oxidized) with the illuminated etch solution, and the modified layer of material is removed. The exposing and removing can be repeated or cycled to etch the material. Further, for oxidation/dissolution embodiments the oxidation and dissolution can occur simultaneously, and the oxidation rate can be greater than the dissolution rate. The material can be a polycrystalline material, a polycrystalline metal, and/or other material. One etch solution can include hydrogen peroxide that is illuminated to form hydroxyl radicals.