# US 2018/0023192 A1 · Compositions and methods using same for carbon doped silicon containing films > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2018/0023192 A1 - Document ID: US20180023192A1 - Status: Published application - Kind: A1 - Application number: 15/548,884 - Filed: 2016-02-04 - Published: 2018-01-25 - Earliest claimed: 2015-02-06 - Assignees: Versum Materials US, LLC - Applicants: Versum Materials US, LLC - Inventors: Haripin Chandra; Kirk Scott Cuthill; Anupama Mallikarjunan; Xinjian Lei; Matthew R. MacDonald; Manchao Xiao; Madhukar Bhaskara Rao; Jianheng Li - Web page: https://patentgrep.com/patent/US20180023192A1 ## CPC - C23C 16/401: {containing silicon} - C23C 14/0605: {Carbon} - C23C 16/345: {Silicon nitride} - C23C 16/36: Carbonitrides - C23C 16/402: {Silicon dioxide} - C23C 16/45536: {Use of plasma, radiation or electromagnetic fields} - C23C 16/56: After-treatment - H10P 14/6336: {in the presence of a plasma [PECVD]} - H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD} - H10P 14/6522: {introduced into a nitride material, e.g. changing SiN to SiON} - H10P 14/6529: {by exposure to a gas or vapour} - H10P 14/6532: {by exposure to a plasma} - H10P 14/6538: {by exposure to UV light} - H10P 14/6539: {by exposure to corpuscular radiation, e.g. exposure to electrons, alpha-particles, protons or ions} - H10P 14/6542: {by using coherent radiation, e.g. using a laser} - H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane} - H10P 14/6687: {the compound comprising silicon and nitrogen} - H10P 14/6922: {the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC} - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract Described herein are compositions and methods using same for forming a silicon-containing film such as, without limitation, a carbon doped silicon oxide film, a carbon doped silicon nitride, a carbon doped silicon oxynitride film in a deposition process. In one aspect, the composition comprises at least cyclic carbosilane having at least one Si—C—Si linkage and at least one anchoring group selected from a halide atom, an amino group, and combinations thereof. ## Claims ### Claim 1 A composition for depositing a silicon containing film, the composition comprising at least one precursor selected from the group consisting of: a cyclic halocarbosilane selected from the group consisting of 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1, 1-diiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-trisilacyclohexane, and 1,3,5-trichloro-1,3,5-trisilacyclohexane; a cyclic haloaminocarbosilane selected from the group consisting of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane, and 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane; and a cyclic aminocarbosilane selected from the group consisting of 1,1,3,3-tetrakis(methylamino)-1,3-disilacyclobutane, 1,1,3,3-tetrakis(dimethylamino)-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(methylamino)-1,3-dimethyl-1,3-disilacyclobutane, and 1,3-bis(iso-propylamino)-1,3-dimethyl-1,3-disilacyclobutane. ### Claim 2 A method for depositing a carbon doped silicon containing film selected from a carbon doped silicon oxide film and a carbon doped silicon oxynitride film, the method comprising: placing a substrate into a reactor; heating the reactor to one or more temperatures ranging from about 2−5100° C. to about 700° C.; introducing at least one cyclic carbosilane precursor selected from the group consisting of a cyclic halocarbosilane, a cyclic haloaminocarbosilane, a cyclic aminocarbosilane and combinations thereof; introducing a nitrogen source under conditions sufficient to react with the at least one cyclic carbosilane precursor and form a carbon doped silicon nitride film; and optionally exposing the silicon carbonitride film to an oxygen source to convert the silicon carbonitride film to the film at one or more temperatures ranging from about 100° C. to 1000° C. ### Claim 3 (depends on 2) The method of claim 2 further comprising treating the silicon containing film with at least one selected from the group consisting of annealing, a plasma, ultraviolet light exposure, laser exposure, electron beam exposure, and combinations thereof. ### Claim 4 (depends on 2) The method of claim 2 wherein the cyclic carbosilane comprises the cyclic halocarbosilane selected from the group consisting of 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1, 1-diiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-trisilacyclohexane, and 1,3,5-trichloro-1,3,5-trisilacyclohexane. ### Claim 5 (depends on 2) The method of claim 2 wherein the cyclic carbosilane comprises the cyclic haloaminocarbosilane selected from the group consisting of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane, and 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane. ### Claim 6 (depends on 2) The method of claim 2 wherein the cyclic carbosilane comprises the cyclic aminocarbosilane selected from the group consisting of 1,1,3,3-tetrakis(methylamino)-1,3-disilacyclobutane, 1,1,3,3-tetrakis(dimethylamino)-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(methylamino)-1,3-dimethyl-1,3-disilacyclobutane, and 1,3-bis(iso-propylamino)-1,3-dimethyl-1,3-disilacyclobutane. ### Claim 7 (depends on 2) The method of claim 2 wherein the film comprises a carbon content of about 10 atomic weight % or greater as measured by XPS. ### Claim 8 (depends on 2) The method of claim 2 wherein the film comprises a wet etch of about 0.15 Å/s or less as measured by dilute hydrofluoric acid. ### Claim 9 A method for depositing a silicon containing film selected from a silicon carbide film and a carbon doped silicon nitride film, the method comprising: placing a semi-conductor substrate into a reactor; heating the reactor to one or more temperatures ranging from about 2−5100° C. to about 700° C. and optionally maintaining the reactor at a pressure of 100 torr or less; introducing at least one cyclic carbosilane selected from the group consisting of a cyclic halocarbosilane, a cyclic haloaminocarbosilane, and combinations thereof; introducing into the reactor a nitrogen-containing plasma source under conditions sufficient to react with the carbosilane precursor and form the film. ### Claim 10 (depends on 9) The method of claim 9 wherein the nitrogen-containing plasma source is selected from the group consisting of nitrogen plasma, a plasma comprising nitrogen and helium, a plasma comprising nitrogen and argon, ammonia plasma, a plasma comprising ammonia and helium, a plasma comprising ammonia and argon, helium plasma, argon plasma, neon plasma, hydrogen plasma, a plasma comprising hydrogen and helium, a plasma comprising hydrogen and argon, an organic amine plasma, organic diamine plasma, and combinations thereof. ### Claim 11 (depends on 9) The method of claim 9 further comprising treating the silicon containing film with at least one selected from the group consisting of annealing, a plasma treatment, ultraviolet light exposure, laser exposure, electron beam exposure, and combinations thereof. ### Claim 12 (depends on 9) The method of claim 9 further comprising exposing the film to an oxygen source into the reactor to convert the silicon containing film into a silicon oxide or carbon doped silicon oxide films. ### Claim 13 (depends on 12) The method of claim 12 wherein the oxygen source is selected from the group consisting of water vapor, water plasma, oxygenated water, oxygenated water steam, oxygen, oxygen plasma, a plasma comprising oxygen and helium, a plasma comprising oxygen and argon plasma, a plasma comprising a nitrogen oxide, a plasma comprising carbon dioxide, hydrogen peroxide, organic peroxides, and combinations thereof. ### Claim 14 (depends on 12) The method of claim 12 wherein the cyclic carbosilane comprises the cyclic halocarbosilane selected from the group consisting of 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1, 1-diiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-trisilacyclohexane, and 1,3,5-trichloro-1,3,5-trisilacyclohexane. ### Claim 15 (depends on 12) The method of claim 12 wherein the cyclic carbosilane comprises the cyclic haloaminocarbosilane selected from the group consisting of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane, and 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane. ### Claim 16 A method for depositing a carbon doped silicon oxide film, the method comprising: placing a substrate into a reactor; introducing at least one cyclic carbosilane precursor having the following Formulae I and II: wherein X1, X2, X3, X4, X5, and X6 are each independently chosen from a hydrogen atom; a halide atom selected from F, Cl, Br, and I; an amino group having the formula NR1R2 wherein R1 and R2 are independently selected from the group consisting of a hydrogen atom, a C1 to C10 linear alkyl group; a C3 to C10 branched alkyl group; a C3 to C10 cyclic alkyl group; a C3 to C10 alkenyl group; a C4 to C10 aryl group; and a C4 to C10 heterocyclic group; introducing a nitrogen source under conditions sufficient to react with the at least one cyclic carbosilane precursor and form a carbon doped silicon nitride film; and, exposing the carbon doped silicon nitride film to an oxygen source under conditions sufficient to convert the carbon doped silicon nitride film to the carbon doped silicon oxide film. ### Claim 17 (depends on 16) The process of claim 16 wherein the precursor comprises Formulae I and X1, X2, X3 and X4 are Cl. ### Claim 18 (depends on 16) The process of claim 16 wherein the exposing comprises thermal annealing the carbon doped silicon nitride film in the presence of the oxygen source. ### Claim 19 (depends on 18) The process of claim 18 wherein the oxygen source comprises at least one of air and water. ### Claim 20 (depends on 16) The process of claim 16 further comprising treating the silicon doped silicon oxide film with a hydrogen containing plasma.