# US 12,114,488 B2 · Enhancing gapfill performance of dram word line > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,114,488 B2 - Document ID: US12114488B2 - Status: Granted - Kind: B2 - Application number: 17/308,577 - Filed: 2021-05-05 - Published: 2022-11-10 - Granted: 2024-10-08 - Earliest claimed: 2021-05-05 - Assignees: Applied Materials, Inc. - Applicants: Applied Materials, Inc. - Inventors: Yong Yang; Kunal Bhatnagar; Srinivas Gandikota; Seshadri Ganguli; Jose Alexandro Romero; Mandyam Sriram; Mohith Verghese; Jacqueline S. Wrench; Yixiong Yang - Web page: https://patentgrep.com/patent/US12114488B2 ## CPC - H10B 12/488: {Word lines} - C23C 16/02: Pretreatment of the material to be coated (C23C16/04 takes precedence) - C23C 16/0272: {Deposition of sub-layers, e.g. to promote the adhesion of the main coating} - C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates} - C23C 16/14: Deposition of only one other metal element - C23C 16/34: Nitrides {(C23C16/303 takes precedence)} - C23C 16/42: Silicides - C23C 16/45523: {Pulsed gas flow or change of composition over time} - C23C 16/45527: {characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations} - C23C 16/45529: {specially adapted for making a layer stack of alternating different compositions or gradient compositions} - C23C 16/45553: {characterized by the use of precursors specially adapted for ALD} - C23C 16/56: After-treatment - H10B 12/053: {the transistor being at least partially in a trench in the substrate (vertical transistor in combination with a capacitor formed in a substrate trench H10B12/0383)} - H10B: ELECTRONIC MEMORY DEVICES - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) ## Abstract Methods of forming memory devices are described. A molybdenum silicide nucleation layer is formed, and the substrate is soaked in a titanium precursor prior to a bulk molybdenum gap fill process. In other embodiments, a molybdenum silicide film is formed in a first process cycle and a second process cycle is performed where the substrate is exposed to a titanium precursor. In further embodiments, a substrate having at least one feature thereon is exposed to a first titanium precursor and a nitrogen-containing reactant. The substrate is then soaked in a second titanium precursor, and then is exposed to a first molybdenum precursor followed by exposure to a silane to form a molybdenum silicide layer on a surface of the substrate. ## Claims ### Claim 1 A method of forming a film, the method comprising: forming a molybdenum-silicide film in a first process cycle comprising sequential exposure of a substrate to a molybdenum precursor, purge gas, a silane precursor, and purge gas, the substrate comprising a plurality of trenches with a gate oxide layer conformally deposited thereon and the molybdenum-silicide film formed in a bottom of the plurality of trenches on the gate oxide layer, the molybdenum precursor comprising one or more of molybdenum chloride (MoCl5), molybdenum fluoride (MoF6), molybdenum iodide (Mol6), molybdenum bromide (MoBr3), molybdenum hexacarbonyl (Mo(CO)6), molybdenum dichloride dioxide (MoO2Cl2), molybdenum oxytetrachloride (MoOCl4), Tetrakis(dimethylamino)molybdenum(IV), and Bis(tert-butylimido)-bis(dimethylamido)molybdenum; and forming a soaked substrate having a titanium species thereon without forming a titanium nitride film in a second process cycle, the second process cycle consisting of flowing a titanium precursor in an atmosphere of argon (Ar) gas over the substrate, and purging the soaked substrate of unreacted titanium precursor, wherein the soaked substrate is formed prior to the first process cycle or wherein the soaked substrate is formed after the first process cycle. ### Claim 2 (depends on 1) The method of claim 1, wherein purging comprises one or more of applying a vacuum or flowing a purge gas over the substrate. ### Claim 3 (depends on 1) The method of claim 1, further comprising exposing the substrate to a second molybdenum precursor and a reactant to fill the plurality of trenches with a bulk molybdenum film. ### Claim 4 (depends on 3) The method of claim 3, further comprising annealing the substrate, wherein the bulk molybdenum film has line bending of less than 2 nm, there is no delamination of the bulk molybdenum film, and the bulk molybdenum film does not have voids. ### Claim 5 A method of forming a film, the method comprising: forming a titanium nitride film in a first process cycle, the first process cycle comprising exposing a substrate to a first titanium precursor and exposing the substrate to a nitrogen-containing reactant, the substrate comprising a plurality of trenches with a gate oxide layer conformally deposited thereon; forming a soaked substrate having a titanium species thereon without forming a titanium nitride film in a second processing cycle, the second processing cycle consisting of flowing a first titanium precursor in an atmosphere of argon (Ar) gas over the substrate, and purging the soaked substrate of unreacted first titanium precursor; and forming a molybdenum-silicide film in a third process cycle comprising sequential exposure of a substrate to a molybdenum precursor, purge gas, a silane reactant, and purge gas, the molybdenum-silicide film formed in a bottom of the plurality of trenches on the gate oxide layer, the molybdenum precursor comprising one or more of molybdenum chloride (MoCl5), molybdenum fluoride (MoF6), molybdenum iodide (Mol6), molybdenum bromide (MoBr3), molybdenum hexacarbonyl (Mo(CO)6), molybdenum dichloride dioxide (MoO2Cl2), molybdenum oxytetrachloride (MoOCl4) Tetrakis(dimethylamino)molybdenum(IV), and Bis(tert-butylimido)-bis(dimethylamido)molybdenum, wherein the first process cycle is performed first, followed by the second process cycle, then the third process cycle. ### Claim 6 (depends on 5) The method of claim 5, further comprising repeating the method to fill the plurality of trenches. ### Claim 7 (depends on 6) The method of claim 6, further comprising annealing the substrate, wherein the molybdenum-silicide film does not have voids. ### Claim 8 A method of forming a memory device, the method comprising: conformally depositing a gate oxide layer on a substrate having a plurality of trenches therein, each trench having a surface, at least one sidewall, and a bottom, the gate oxide layer forming on the surface, along the at least one sidewall, and on the bottom of the trench; forming a work function metal layer comprising titanium nitride on the gate oxide layer by exposing the substrate to a first titanium precursor and a nitrogen-containing reactant to form the work function metal layer; forming a soaked substrate having a titanium species thereon without forming a titanium nitride layer in a process cycle, the process cycle consisting of flowing a second titanium precursor in an atmosphere of argon (Ar) gas over the substrate, and purging the soaked substrate of unreacted second titanium precursor, wherein the soaked substrate is formed after forming the work function metal layer; exposing the substrate to a first molybdenum precursor and a silane reactant to form a molybdenum silicide nucleation layer on the soaked substrate; exposing the substrate to a second molybdenum precursor and a reactant to fill the plurality of trenches with a bulk molybdenum film; annealing the substrate, wherein the bulk molybdenum film has line bending of less than 2 nm, there is no delamination of the bulk molybdenum film, and the bulk molybdenum film does not have voids; and recessing the annealed bulk molybdenum film to form a buried word line. ### Claim 9 (depends on 8) The method of claim 8, wherein the substrate is exposed to the first molybdenum precursor and the silane reactant sequentially. ### Claim 10 (depends on 8) The method of claim 8, wherein the substrate is exposed to the first molybdenum precursor and the silane reactant simultaneously. ### Claim 11 (depends on 8) The method of claim 8, further comprising purging the surface of the substrate of the second titanium precursor prior to exposing the substrate to the first molybdenum precursor. ### Claim 12 (depends on 11) The method of claim 11, wherein purging comprises one or more of applying a vacuum or flowing a purge gas over the substrate. ### Claim 13 (depends on 12) The method of claim 12, wherein the purge gas comprises one or more of nitrogen (N2), helium (He), and argon (Ar).