# US 10,312,108 B2 · Method for forming semiconductor structure using modified resist layer > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,312,108 B2 - Document ID: US10312108B2 - Status: Granted - Kind: B2 - Application number: 15/480,976 - Filed: 2017-04-06 - Published: 2018-10-11 - Granted: 2019-06-04 - Earliest claimed: 2017-04-06 - Assignees: Taiwan Semiconductor Manufacturing Company, Ltd. - Applicants: Taiwan Semiconductor Manufacturing Co., Ltd. - Inventors: Li-Po Yang; Chien-Wei Wang; Wei-Han Lai; Chin-Hsiang Lin - Web page: https://patentgrep.com/patent/US10312108B2 ## CPC - H10P 50/73: {using masks for insulating materials} - G03F 7/0752: {in non photosensitive layers or as additives, e.g. for dry lithography} - G03F 7/405: {Treatment with inorganic or organometallic reagents after imagewise removal} - H10P 76/204: {of organic photoresist masks} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) ## Abstract Methods for forming a semiconductor structure are provided. The method for forming a semiconductor structure includes forming a material layer over a substrate and forming a resist layer over the material layer. The method for forming a semiconductor structure further includes exposing the resist layer to form an exposed portion of the resist layer and forming a treating material layer over the exposed portion and an unexposed portion of the resist layer. In addition, a top surface of the exposed portion of the resist layer reacts with the treating material layer. The method for forming a semiconductor structure further includes removing the treating material layer and removing the unexposed portion of the resist layer to form an opening in the resist layer after the treating material is removed. ## Claims ### Claim 1 A method for forming a semiconductor structure, comprising: forming a material layer over a substrate; forming a resist layer over the material layer; exposing the resist layer to form an exposed portion of the resist layer; forming a treating material layer over the exposed portion and an unexposed portion of the resist layer, wherein a top surface of the exposed portion of the resist layer reacts with the treating material layer to form a modified exposed portion; removing the treating material layer; and removing the unexposed portion of the resist layer to form an opening in the resist layer after the treating material is removed. ### Claim 2 (depends on 1) The method for forming a semiconductor structure as claimed in claim 1, wherein the treating material layer comprises a treating compound, and the treating compound bonds to the top surface of the exposed portion of the resist layer through an amine group. ### Claim 3 (depends on 1) The method for forming a semiconductor structure as claimed in claim 1, wherein the treating layer comprises a treating compound having the following formula: wherein R1 is C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C5-C20 aryl, or C5-C20 heteroaryl; R2 is C1-C20 alkoxy, hydroxyl, hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C5-C20 aryl, or C4-C20 heteroaryl; R3 is C1-C20 alkoxy, hydroxyl, hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C5-C20 aryl, or C4-C20 heteroaryl; and R4 is C1-C20 alkoxy, hydroxyl, hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C5-C20 aryl, or C4-C20 heteroaryl. ### Claim 4 (depends on 1) The method for forming a semiconductor structure as claimed in claim 1, wherein the treating material layer comprises a silicon-containing treating compound, and the silicon-containing treating compound comprises about 5 wt % to about 46 wt % of Si. ### Claim 5 (depends on 1) The method for forming a semiconductor structure as claimed in claim 1, wherein the step of removing the unexposed portion of the resist layer to form an opening in the resist layer comprises: dissolving the unexposed portion of the resist layer in a developer. ### Claim 6 A method for forming a semiconductor structure, comprising: forming a material layer over a substrate; forming a resist layer having a first portion and a second portion over the material layer; exposing the first portion of the resist layer while the second portion of the resist layer remains unexposed; forming a treating material layer over the resist layer to modify a top surface of the first portion of the resist layer; removing the treating material layer; dissolving the second portion of the resist layer in a developer to form an opening after the modified first portion is formed; and etching the material layer through the opening, wherein the treating material layer comprises a silicon-containing treating compound. ### Claim 7 (depends on 6) The method for forming a semiconductor structure as claimed in claim 6, further comprising: baking the resist layer after the first portion of the resist layer is exposed. ### Claim 8 (depends on 7) The method for forming a semiconductor structure as claimed in claim 7, further comprising: baking the resist layer after the treating material layer is formed. ### Claim 9 (depends on 6) The method for forming a semiconductor structure as claimed in claim 6, wherein the silicon-containing treating compound reacts with the top surface of the first portion of the resist layer in an acid-base reaction. ### Claim 10 (depends on 6) The method for forming a semiconductor structure as claimed in claim 6, wherein the silicon-containing treating compound has the following formula: wherein R1 is C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C5-C20 aryl, or C5-C20 heteroaryl; R2 is C1-C20 alkoxy, hydroxyl, hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C5-C20 aryl, or C4-C20 heteroaryl; R3 is C1-C20 alkoxy, hydroxyl, hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C5-C20 aryl, or C4-C20 heteroaryl; and R4 is C1-C20 alkoxy, hydroxyl, hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C5-C20 aryl, or C4-C20 heteroaryl. ### Claim 11 (depends on 10) The method for forming a semiconductor structure as claimed in claim 10, wherein the amine group in the silicon-containing treating compound reacts with an acid group at the top surface of the first portion of the resist layer when the treating material layer is formed over the resist layer. ### Claim 12 (depends on 6) The method for forming a semiconductor structure as claimed in claim 6, wherein the silicon-containing treating compound comprises about 5 wt % to about 46 wt % of Si. ### Claim 13 A method for forming a semiconductor structure, comprising: forming a material layer over a substrate; forming a resist layer over the material layer; exposing a first portion of the resist layer; reacting a treating compound with a top surface of the first portion of the resist layer to form a modified first portion of the resist layer, wherein the treating compound has the following formula: wherein R1 is C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C5-C20 aryl, or C5-C20 heteroaryl; R2 is C1-C20 alkoxy, hydroxyl, hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C5-C20 aryl, or C4-C20 heteroaryl; R3 is C1-C20 alkoxy, hydroxyl, hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C5-C20 aryl, or C4-C20 heteroaryl; and R4 is C1-C20 alkoxy, hydroxyl, hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C5-C20 aryl, or C4-C20 heteroaryl. ### Claim 14 (depends on 13) The method for forming a semiconductor structure as claimed in claim 13, wherein the treating compound bonds to the top surface of the first portion of the resist layer through its amine group. ### Claim 15 (depends on 13) The method for forming a semiconductor structure as claimed in claim 13, wherein R1 is C1-C5 alkyl, R2, R3, and R4 are C1-C5 alkoxy or hydroxyl. ### Claim 16 (depends on 13) The method for forming a semiconductor structure as claimed in claim 13, wherein a molecular weight of the treating compound is in a range from about 100 to about 10000. ### Claim 17 (depends on 13) The method for forming a semiconductor structure as claimed in claim 13, further comprising: removing an unexposed portion of the resist layer after the modified first portion of the resist layer is formed. ### Claim 18 (depends on 13) The method for forming a semiconductor structure as claimed in claim 13, further comprising: removing an unexposed portion of the resist layer before the modified first portion of the resist layer is formed, such that the treating compound also reacts with sidewalls of the first portion of the resist layer. ### Claim 19 (depends on 13) The method for forming a semiconductor structure as claimed in claim 13, wherein the step of reacting a treating compound with a top surface of the first portion of the resist layer comprises coating a treating material layer over the resist layer; and removing the treating material layer after the modified first portion of the resist layer is formed, wherein the treating material layer comprises the treating compound, and a concentration of the treating compound in the treating material layer is in a range from about 0.001 wt % to about 10 wt %. ### Claim 20 (depends on 1) The method for forming a semiconductor structure as claimed in claim 1, further comprising; etching the material layer through the opening of the resist layer; and removing the exposed portion of the resist layer after the material layer is etched.