# US 12,112,938 B2 · Semiconductor processing preclean methods and apparatus > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,112,938 B2 - Document ID: US12112938B2 - Status: Granted - Kind: B2 - Application number: 17/655,245 - Filed: 2022-03-17 - Published: 2022-09-22 - Granted: 2024-10-08 - Earliest claimed: 2021-03-18 - Assignees: ASM IP Holding B.V. - Applicants: Asm IP Holding B.V. - Inventors: Chuang Wei; Aditya Chaudhury; Prahlad Kulkarni; Xing Lin; Xiaoda Sun; Woo Jung Shin; Bubesh Babu Jotheeswaran; Fei Wang; Qu Jin; Aditya Walimbe; Rajeev Reddy Kosireddy; Yen Chun Fu; Amin Azimi - Web page: https://patentgrep.com/patent/US12112938B2 ## CPC - H10P 70/12: {by dry cleaning only (H10P70/52 takes precedence)} - H10P 70/125: {with gaseous HF} - B08B 5/00: Cleaning by methods involving the use of air flow or gas flow (cleaning hollow articles by methods or apparatus specially adapted thereto B08B9/00) - H01J 37/32357: {Generation remote from the workpiece, e.g. down-stream} - H01J 37/32449: {Gas control, e.g. control of the gas flow} - H10P 50/283: {by chemical means} - H10P 72/0402: {Apparatus for fluid treatment (H10P72/0441, H10P72/0448 take precedence)} - H10P 72/0421: {for drying etching} - H01J 2237/335: Cleaning - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - B08B: CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL - H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H) ## Abstract In some embodiments, a method for semiconductor processing preclean includes removing an oxide layer from a substrate using anhydrous hydrogen fluoride in combination with water vapor. A system for the preclean may be configured to separate the anhydrous hydrogen fluoride and the water vapor until they are delivered to a common volume near the substrate. Corrosion within components of the system may be limited by purification of anhydrous hydrogen fluoride, passivation of components, changing component materials, and heating components. Passivation may be achieved by filling a gas delivery component with anhydrous hydrogen fluoride and allowing the anhydrous hydrogen fluoride to remain in the gas delivery component to form a passivation layer. Consistent water vapor delivery may be achieved in part by heating components using heaters. ## Claims ### Claim 1 A semiconductor processing system for precleaning a substrate, the system comprising: a reaction chamber; an anhydrous hydrogen fluoride delivery system comprising: an upstream portion configured to be in fluid communication with an anhydrous hydrogen fluoride source, the upstream portion comprising: a pressure gauge configured to be in fluid communication with the anhydrous hydrogen fluoride source; a purifier in fluid communication with the pressure gauge and configured to remove water from anhydrous hydrogen fluoride from the anhydrous hydrogen fluoride source; a first anhydrous hydrogen fluoride conduit for forming a first portion of a flow path between the anhydrous hydrogen fluoride source and the reaction chamber; a mass flow controller configured to be in fluid communication with the first anhydrous hydrogen fluoride conduit and the first portion of the flow path; and one or more upstream heater jackets thermally coupled to the pressure gauge, the purifier, the first anhydrous hydrogen fluoride conduit, and the mass flow controller; a downstream portion downstream from and in fluid communication with the upstream portion, the downstream portion comprising: a second anhydrous hydrogen fluoride conduit for forming a second portion of the flow path between the anhydrous hydrogen fluoride source and the reaction chamber, the second anhydrous hydrogen fluoride conduit being connected to the mass flow controller and configured to fluidly connect, via the mass flow controller, the upstream portion with the reaction chamber; and one or more downstream heater jackets thermally coupled to the second anhydrous hydrogen fluoride conduit; a water vapor delivery system comprising: a water vapor source in fluid communication with a carrier gas source and configured to supply water vapor; a water vapor supply conduit disposed downstream of the water vapor source and forming a portion of a flow path between the water vapor source and the reaction chamber; a carrier gas conduit disposed upstream of the water vapor source and configured to be in fluid communication with the carrier gas source and the water vapor source; one or more water vapor source heater jackets thermally coupled to the water vapor source; one or more water vapor supply heater jackets disposed downstream of the one or more water vapor source heater jackets and thermally coupled to the water vapor supply conduit; and a pressure flow controller disposed upstream of the water vapor source and the one or more water vapor source heater jackets and configured to be in fluid communication with the carrier gas source and the water vapor source, the pressure flow controller configured to regulate a pressure of carrier gas from the carrier gas source flowing to the water vapor source via the carrier gas conduit; and a reducing conduit in fluid communication with the anhydrous hydrogen fluoride delivery system and the water vapor delivery system, wherein the reaction chamber is in fluid communication with the reducing conduit. ### Claim 2 (depends on 1) The system of claim 1, further comprising a remote plasma unit connected to the reducing conduit, and in fluid communication therethrough with, the anhydrous hydrogen fluoride delivery system, the water vapor delivery system, and the reaction chamber. ### Claim 3 (depends on 2) The system of claim 2, further comprising: a showerhead disposed inside the reaction chamber and configured to distribute anhydrous hydrogen fluoride and water vapor inside the reaction chamber; and a susceptor configured to support the substrate within the reaction chamber, wherein the susceptor comprises a susceptor heating element. ### Claim 4 (depends on 1) The system of claim 1, wherein the one or more upstream heater jackets and the one or more downstream heater jackets are form-fitted to the upstream portion and the downstream portion, respectively. ### Claim 5 (depends on 1) The system of claim 1, wherein the anhydrous hydrogen fluoride delivery system further comprises a controller configured to control one or more temperatures of the one or more upstream heater jackets, one or more temperatures of the one or more downstream heater jackets, and a flow rate of anhydrous hydrogen fluoride into the reaction chamber. ### Claim 6 (depends on 5) The system of claim 5, wherein the controller is programmed to maintain the downstream portion at a higher temperature than the upstream portion. ### Claim 7 (depends on 5) The system of claim 5, wherein the anhydrous hydrogen fluoride delivery system further comprises: a vent portion comprising: a vent conduit connected to the second anhydrous hydrogen fluoride conduit; and a vent heater jacket thermally coupled to the vent conduit, wherein the controller is programmed to maintain the vent conduit at a temperature greater than the temperature of the downstream portion. ### Claim 8 (depends on 1) The system of claim 1, wherein the water vapor delivery system further comprises: a vent conduit fluidly connected to the water vapor supply conduit; one or more vent heater jackets thermally coupled to the vent conduit; and a controller configured to control one or more temperatures of the one or more water vapor source heater jackets and one or more temperatures of the one or more water vapor supply heater jackets, wherein the controller is further configured to control one or more temperatures of the one or more vent heater jackets. ### Claim 9 (depends on 1) The system of claim 1, wherein the water vapor delivery system further comprises: a bleed conduit in fluid communication with the carrier gas source and the water vapor source, the bleed conduit configured to reduce backstreaming of one or more of the water vapor or the carrier gas. ### Claim 10 (depends on 1) The system of claim 1, wherein the water vapor source comprises a space for liquid water and an overlying ullage space for water vapor. ### Claim 11 (depends on 1) The system of claim 1, wherein the one or more water vapor supply heater jackets is configured to heat the water vapor supply conduit to a temperature of at least 40 degrees Celsius greater than the temperature of the water vapor source.