# US 10,504,779 B2 · Hydrogenation and nitridization processes for reducing oxygen content in a film > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,504,779 B2 - Document ID: US10504779B2 - Status: Granted - Kind: B2 - Application number: 16/260,084 - Filed: 2019-01-28 - Published: 2019-05-23 - Granted: 2019-12-10 - Earliest claimed: 2016-06-20 - Assignees: Applied Materials, Inc. - Applicants: Applied Materials, Inc. - Inventors: Johanes S. Swenberg; Wei Liu; Houda Graoui; Shashank Sharma; Shankar Muthukrishnan; Rene George - Web page: https://patentgrep.com/patent/US10504779B2 ## CPC - H10W 20/048: {by using plasmas or gaseous environments, e.g. by nitriding} - H10D 64/0112: {using conductive layers comprising silicides} - H10D 64/01125: {the silicides being formed by chemical reaction with the semiconductor after the contact hole formation} - H10P 14/418: {the conductive layers comprising transition metals} - H10P 14/43: Chemical deposition, e.g. chemical vapour deposition [CVD] - H10W 20/033: {in openings in dielectrics} - H10W 20/038: {covering conductive structures (H10W20/037 takes precedence)} - H10W 20/047: {by introducing additional elements therein} - H10W 20/0523: {by irradiating with ultraviolet or particle radiation} - H10W 20/066: {by forming silicides of refractory metals} - H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10 - H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract Embodiments described herein generally relate to a sequential hydrogenation and nitridization process for reducing interfacial and bulk O atoms in a conductive structure in a semiconductor device. A hydrogenation and plasma nitridization process is performed on a metal nitride layer in a conductive structure prior to deposition of a second metal layer, thereby reducing interfacial oxygen atoms formed on a surface of the metal nitride and oxygen atoms present in the bulk metal layers of the conductive structure. As a result, adhesion of the second metal layer to the metal nitride layer is improved and the electrical resistance of the contact structure is reduced. ## Claims ### Claim 1 A method of forming a structure in a semiconductor device, comprising: performing an oxygen-free plasma treatment process on a processing chamber component disposed within a processing chamber in which the processing chamber component is exposed to a non-oxidizing plasma comprising hydrogen; depositing a metal layer on a substrate within the processing chamber, the metal layer comprising oxygen; exposing a surface of the metal layer to a non-oxidizing plasma comprising hydrogen, while a first biasing voltage is applied to the substrate; and exposing the exposed surface of the metal layer to a plasma comprising nitrogen, while a second biasing voltage is applied to the substrate. ### Claim 2 (depends on 1) The method of claim 1, wherein the first biasing voltage is between about 175 V and about 250 V, and the second biasing voltage is between about 175 V and about 250 V. ### Claim 3 (depends on 1) The method of claim 1, wherein the exposed surface of the metal layer is not exposed to air after being exposed to the non-oxidizing plasma comprising hydrogen and before being exposed to the plasma comprising nitrogen. ### Claim 4 (depends on 1) The method of claim 1, wherein the metal layer comprises nitrogen. ### Claim 5 (depends on 1) The method of claim 1, wherein the plasma comprising nitrogen consists essentially of ammonia, nitrogen gas, and argon. ### Claim 6 (depends on 1) The method of claim 1, further comprising, prior to depositing the metal layer, performing a surface preparation process on a surface of the substrate. ### Claim 7 (depends on 1) The method of claim 1, wherein the non-oxidizing plasma comprising hydrogen consists essentially of hydrogen gas and argon gas. ### Claim 8 (depends on 1) The method of claim 1, further comprising exposing the metal layer to the non-oxidizing plasma comprising hydrogen and the plasma comprising nitrogen a second time. ### Claim 9 (depends on 1) The method of claim 1, wherein the oxygen-free plasma treatment process is performed on the processing chamber component when the substrate is not disposed within the processing chamber. ### Claim 10 A method of forming a structure in a semiconductor device, comprising: performing an oxygen-free plasma treatment process on a processing chamber component disposed within a processing chamber in which the processing chamber component is exposed to a non-oxidizing plasma comprising hydrogen; depositing a metal layer on a substrate within the processing chamber, the metal layer comprising oxygen; exposing a surface of the metal layer to a non-oxidizing plasma comprising hydrogen, while a first bias is applied to the substrate; exposing the exposed surface of the metal layer to a plasma comprising nitrogen, while a second bias is applied to the substrate; and performing a thermal anneal process on the metal layer. ### Claim 11 (depends on 10) The method of claim 10, wherein the first biasing voltage is between about 175 V and about 250 V, and the second biasing voltage is between about 175 V and about 250 V. ### Claim 12 (depends on 10) The method of claim 10, wherein the exposed surface of the metal layer is not exposed to air after being exposed to the non-oxidizing plasma comprising hydrogen and before being exposed to the plasma comprising nitrogen. ### Claim 13 (depends on 10) The method of claim 10, wherein the metal layer comprises nitrogen. ### Claim 14 (depends on 10) The method of claim 10, wherein the plasma comprising nitrogen consists essentially of ammonia, nitrogen gas, and argon. ### Claim 15 (depends on 10) The method of claim 10, further comprising, prior to depositing the metal layer, performing a surface preparation process on a surface of the substrate. ### Claim 16 (depends on 10) The method of claim 10, wherein the non-oxidizing plasma comprising hydrogen consists essentially of hydrogen gas and argon gas. ### Claim 17 (depends on 10) The method of claim 10, further comprising exposing the metal layer to the non-oxidizing plasma comprising hydrogen and the plasma comprising nitrogen a second time. ### Claim 18 (depends on 10) The method of claim 10, wherein the oxygen-free plasma treatment process is performed on the processing chamber component when the substrate is not disposed within the processing chamber. ### Claim 19 A method of forming a structure in a semiconductor device, the method comprising: performing an oxygen-free plasma treatment process on a processing chamber component disposed within a processing chamber in which the processing chamber component is exposed to a non-oxidizing plasma comprising hydrogen; depositing a metal layer on a substrate within the processing chamber, the metal layer comprising oxygen; exposing a surface of the metal layer to a non-oxidizing plasma comprising hydrogen, while a first biasing voltage is applied to the substrate; and exposing the exposed surface of the metal layer to a plasma comprising nitrogen and having an RF power of about 100 W to about 2,500 W, while a second biasing voltage is applied to the substrate. ### Claim 20 (depends on 19) The method of claim 19, wherein the first biasing voltage is between about 175 V and about 250 V, and the second biasing voltage is between about 175 V and V to about 250 V, and the RF power is about 1,000 W to about 2,000 W.