# US 11,306,249 B2 · Substrate processing method, substrate processing device and etching liquid > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,306,249 B2 - Document ID: US11306249B2 - Status: Granted - Kind: B2 - Application number: 16/965,776 - Filed: 2019-01-23 - Published: 2021-02-04 - Granted: 2022-04-19 - Earliest claimed: 2018-01-30 - Assignees: Tokyo Electron Limited - Applicants: Tokyo Electron Limited - Inventors: Koukichi Hiroshiro; Tetsuya Sakazaki; Koji Kagawa; Kenji Sekiguchi; Kazuyoshi Mizumoto - Web page: https://patentgrep.com/patent/US11306249B2 ## CPC - C09K 13/08: containing a fluorine compound - H10P 72/0456: {in-line arrangement} - H10P 50/283: {by chemical means} - H10P 50/667: {by liquid etching only} - H10P 70/23: {during, before or after processing of insulating materials} - H10P 70/273: {the processing being a delineation of conductive layers, e.g. by RIE} - H10P 72/0402: {Apparatus for fluid treatment (H10P72/0441, H10P72/0448 take precedence)} - H10P 72/0406: {for cleaning followed by drying, rinsing, stripping, blasting or the like} - H10P 72/0424: {using mainly spraying means, e.g. nozzles} - H10P 72/0426: {with the semiconductor substrates being dipped in baths or vessels} - H10P 72/7618: {characterised by a movable susceptor, stage or support, others than those only rotating on their own vertical axis, e.g. susceptors on a rotating carrousel} - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract A substrate processing method includes holding a substrate; and supplying an etching liquid to the substrate held in the holding of the substrate. The etching liquid contains an etching agent configured to etch a metal-based first material and a silicon-based second material exposed on the substrate and a protection agent configured to react with the second material between the first material and the second material to form a protection layer on a surface of the second material. Here, the etching agent is a liquid which contains fluorine atoms and an organic solvent and substantially does not contain water, and the protection layer protects the second material from etching with the etching agent. ## Claims ### Claim 1 A substrate processing method, comprising: holding a substrate; and supplying an etching liquid to the substrate held in the holding of the substrate, the etching liquid containing an etching agent configured to etch a metal-based first material and a silicon-based second material exposed on the substrate and a protection agent configured to react with the silicon-based second material between the metal-based first material and the silicon-based second material to form a protection layer on a surface of the silicon-based second material, the etching agent being a liquid which contains fluorine atoms and an organic solvent and substantially does not contain water, and the protection layer protecting the silicon-based second material from etching with the etching agent, and separating the organic solvent from a used etching liquid serving as the etching liquid in the supplying of the etching liquid, wherein the separating of the organic solvent includes: discharging the used etching liquid to a first drain line configured to discharge a processing liquid; and vaporizing the organic solvent contained in the used etching liquid by heating the used etching liquid flowing through the first drain line. ### Claim 2 (depends on 1) The substrate processing method of claim 1, wherein the protection agent is a silylating agent. ### Claim 3 (depends on 1) The substrate processing method of claim 1, wherein the protection agent has a direct bond between a silicon atom and a nitrogen atom. ### Claim 4 (depends on 3) The substrate processing method of claim 3, wherein the protection agent is represented by a following Chemical Formula 1: and R1 to R5 each independently represent an alkyl group substituted with a halogen or an unsubstituted alkyl group. ### Claim 5 (depends on 3) The substrate processing method of claim 3, wherein the protection agent is represented by a following Chemical Formula 2: and R6 to R12 each independently represent an alkyl group or a hydrogen atom. ### Claim 6 (depends on 3) The substrate processing method of claim 3, wherein the protection agent is represented by a following Chemical Formula 3: and R13 to R19 each independently represent an alkyl group. ### Claim 7 (depends on 1) The substrate processing method of claim 1, wherein the first drain line is configured to discharge the processing liquid other than an organic processing liquid, wherein the separating of the organic solvent further includes: discharging the organic solvent, which is vaporized in the vaporizing of the organic solvent, to a second drain line through a connection line configured to connect the second drain line configured to discharge the organic processing liquid and the first drain line. ### Claim 8 (depends on 7) The substrate processing method of claim 7, wherein a boiling point of the organic solvent is lower than a boiling point of water, and in the vaporizing of the organic solvent, the used etching liquid is heated to a temperature lower than the boiling point of the water and higher than the boiling point of the organic solvent. ### Claim 9 (depends on 7) The substrate processing method of claim 7, wherein the discharging of the organic solvent includes: liquefying the organic solvent, which is vaporized in the vaporizing of the organic solvent, in the connection line. ### Claim 10 (depends on 7) The substrate processing method of claim 7, further comprising: dissolving and discharging a salt containing the fluorine atoms and remaining in the first drain line by allowing a cleaning liquid configured to dissolve the salt to flow into the first drain line. ### Claim 11 (depends on 1) The substrate processing method of claim 1, wherein the separating of the organic solvent includes: discharging the used etching liquid to a first drain line configured to discharge a processing liquid other than an organic processing liquid and storing the used etching liquid in a reservoir provided at a portion of the first drain line; vaporizing the organic solvent contained in the used etching liquid by heating the used etching liquid stored in the reservoir; and discharging the organic solvent, which is vaporized in the vaporizing of the organic solvent, to a second drain line through a connection line configured to connect the second drain line configured to discharge the organic processing liquid and the reservoir. ### Claim 12 (depends on 1) The substrate processing method of claim 1, wherein the etching agent is generated by dissolving a salt containing the fluorine atoms in the organic solvent.