# US 11,443,953 B2 · Method for forming and using stress-tuned silicon oxide films in semiconductor device patterning > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,443,953 B2 - Document ID: US11443953B2 - Status: Granted - Kind: B2 - Application number: 16/682,607 - Filed: 2019-11-13 - Published: 2020-05-14 - Granted: 2022-09-13 - Earliest claimed: 2018-11-13 - Assignees: Tokyo Electron Limited - Applicants: Tokyo Electron Limited - Inventors: Kandabara N. Tapily; Anton deVilliers; Gerrit J. Leusink - Web page: https://patentgrep.com/patent/US11443953B2 ## CPC - H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD} - H10P 50/283: {by chemical means} - H10P 14/662: {Laminate layers, e.g. stacks of alternating high-k metal oxides (adhesion layers or buffer layers H10P14/6508, H10P14/6548)} - H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane} - H10P 14/6686: {the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane} - H10P 14/69215: {the material being a silicon oxide, e.g. SiO2} - H10P 14/69391: {the material containing aluminium, e.g. Al2O3} - H10P 76/4085: {characterised by the processes involved to create the masks} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract A processing method includes receiving a substrate containing a base layer having a mandrel pattern formed thereon containing a number of features, conformally depositing a silicon oxide film over the mandrel pattern by coating surfaces of the substrate with a metal-containing catalyst layer, and in the absence of any oxidizing and hydrolyzing agent, exposing the substrate to a process gas containing a silanol gas at a substrate temperature selected to yield a preferred level of stress in the silicon oxide film. The method further includes removing the silicon oxide film from upper surfaces of the mandrel pattern and lower surfaces adjacent the mandrel pattern to leave behind silicon oxide sidewall spacers on sidewalls of the mandrel pattern, and removing the mandrel pattern from the substrate to leave behind the silicon oxide sidewall spacers that form a new pattern having double the number of features of the removed mandrel pattern. ## Claims ### Claim 1 A method for processing a substrate, the method comprising: receiving a substrate containing a base layer having a mandrel pattern formed thereon containing a number of features; conformally depositing a silicon oxide film over the mandrel pattern by coating surfaces of the substrate with a metal-containing catalyst layer, and in the absence of any oxidizing and hydrolyzing agent, exposing the substrate to a process gas containing a silanol gas at a substrate temperature that is selected to yield a preferred level of stress in the silicon oxide film; repeating the coating and exposing steps at least once to increase a thickness of the silicon oxide film; removing the silicon oxide film from upper surfaces of the mandrel pattern and lower surfaces adjacent the mandrel pattern to leave behind silicon oxide sidewall spacers on sidewalls of the mandrel pattern; removing the mandrel pattern from the substrate to leave behind the silicon oxide sidewall spacers that form a new pattern having double the number of features of the removed mandrel pattern; conformally depositing a metal oxide film on the new pattern; removing the metal oxide film from upper surfaces of the new pattern and lower surfaces adjacent the new pattern to leave behind metal oxide sidewall spacers on sidewalls of the new pattern; and removing the silicon oxide sidewall spacers from the substrate to leave behind the metal oxide sidewall spacers that form a second new pattern having double the number of features of the removed new pattern. ### Claim 2 (depends on 1) The method of claim 1, wherein the substrate temperature is between about 200° C. and about 750° C. and the silicon oxide film has tensile stress. ### Claim 3 (depends on 1) The method of claim 1, wherein the substrate temperature is less than about 200° C. or greater than about 750° C. and the silicon oxide film has compressive stress. ### Claim 4 (depends on 1) The method of claim 1, wherein the substrate temperature is about 200° C. or about 750° C. and the silicon oxide film is unstressed. ### Claim 5 (depends on 1) The method of claim 1, wherein the the metal-containing catalyst layer is selected from the group consisting of Al, Al2O3, AlN, AlON, an Al-containing precursor, Al-alloys, CuAl, TiAlN, TaAlN, Ti, TiAlC, TiO2, TiON, TiN, a Ti-containing precursor, Ti-alloys, a Hf containing precursor, a Zr-containing precursor, and combinations thereof. ### Claim 6 (depends on 1) The method of claim 1, wherein the silanol gas is selected from the group consisting of tris(tert-pentoxy) silanol (TPSOL), tris(tert-butoxy) silanol, and bis(tert-butoxy)(isopropoxy) silanol. ### Claim 7 (depends on 1) The method of claim 1, wherein the silicon oxide film forms a mixture with a metal oxide containing TiO2, Al2O3, HfO2, ZrO2, or a combination thereof. ### Claim 8 (depends on 1) The method of claim 1, wherein the preferred level of stress in the silicon oxide film improves the vertical profiles of the silicon oxide sidewall spacers. ### Claim 9 (depends on 1) The method of claim 1, wherein the metal oxide film contains TiO2, Al2O3, HfO2, ZrO2, or a combination thereof. ### Claim 10 (depends on 1) The method of claim 1, further comprising: transferring the second new pattern into the base layer; and removing the metal oxide sidewall spacers from the substrate. ### Claim 11 A method for processing a substrate, the method comprising: receiving a substrate containing a base layer having a mandrel pattern formed thereon comprising a number of features; conformally depositing a silicon oxide film over the mandrel pattern by: coating surfaces of the substrate with a metal-containing catalyst layer, and in the absence of any oxidizing and hydrolyzing agent, exposing the substrate to a process gas containing a silanol gas at a substrate temperature that is selected to yield a preferred level of stress in the silicon oxide film; conformally depositing a metal oxide film on the silicon oxide film; thereafter, removing the metal oxide film and the silicon oxide film from upper surfaces of the mandrel pattern and lower surfaces adjacent the mandrel pattern to leave behind metal oxide sidewall spacers and silicon oxide sidewall spacers on sidewalls of the mandrel pattern; and removing the mandrel pattern from the substrate to leave behind the metal oxide sidewall spacers and the silicon oxide sidewall spacers that form a new pattern having double the number of features of the removed mandrel pattern. ### Claim 12 (depends on 11) The method of claim 11, wherein the substrate temperature is between about 200° C. and about 750° C. and the silicon oxide film has tensile stress. ### Claim 13 (depends on 11) The method of claim 11, wherein the substrate temperature is less than about 200° C. or greater than about 750° C. and the silicon oxide film has compressive stress. ### Claim 14 (depends on 11) The method of claim 11, wherein the substrate temperature is about 200° C. or about 750° C. and the silicon oxide film is unstressed. ### Claim 15 (depends on 11) The method of claim 11, wherein the the metal-containing catalyst layer is selected from the group consisting of Al, Al2O3, AlN, AlON, an Al-containing precursor, Al-alloys, CuAl, TiAlN, TaAlN, Ti, TiAlC, TiO2, TiON, TiN, a Ti-containing precursor, Ti-alloys, a Hf containing precursor, a Zr-containing precursor, and combinations thereof. ### Claim 16 (depends on 11) The method of claim 11, wherein the silanol gas is selected from the group consisting of tris(tert-pentoxy) silanol (TPSOL), tris(tert-butoxy) silanol, and bis(tert-butoxy)(isopropoxy) silanol. ### Claim 17 (depends on 11) The method of claim 11, wherein the metal oxide film contains TiO2, Al2O3, HfO2, ZrO2, or a combination thereof. ### Claim 18 (depends on 11) The method of claim 11, further comprising: transferring the new pattern into the base layer; and removing the metal oxide sidewall spacers and the silicon oxide sidewall spacers from the substrate. ### Claim 19 A method for processing a substrate, the method comprising: receiving a substrate containing a base layer having a mandrel pattern formed thereon containing a number of features; conformally depositing a silicon oxide film over the mandrel pattern by coating surfaces of the substrate with a metal-containing catalyst layer, and in the absence of any oxidizing and hydrolyzing agent, exposing the substrate to a process gas containing a silanol gas at a substrate temperature that is selected to yield a preferred level of stress in the silicon oxide film; removing the silicon oxide film from upper surfaces of the mandrel pattern and lower surfaces adjacent the mandrel pattern to leave behind silicon oxide sidewall spacers on sidewalls of the mandrel pattern; removing the mandrel pattern from the substrate to leave behind the silicon oxide sidewall spacers that form a new pattern having double the number of features of the removed mandrel pattern; conformally depositing a metal oxide film on the new pattern; removing the metal oxide film from upper surfaces of the new pattern and lower surfaces adjacent the new pattern to leave behind metal oxide sidewall spacers on sidewalls of the new pattern; and removing the silicon oxide sidewall spacers from the substrate to leave behind the metal oxide sidewall spacers that form a second new pattern having double the number of features of the removed new pattern. ### Claim 20 (depends on 19) The method of claim 19, wherein the metal oxide film contains TiO2, Al2O3, HfO2, ZrO2, or a combination thereof.