# US 5,348,587 A · Apparatus for elimination of low temperature ammonia salts in TiCl.sub.4 NH.sub.3 CVD reaction > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,348,587 A - Document ID: US5348587A - Status: Granted - Kind: A - Application number: 08/133,582 - Filed: 1993-10-07 - Granted: 1994-09-20 - Earliest claimed: 1992-11-16 - Assignees: Materials Research Corporation - Inventors: Eric C. Eichman; Bruce A. Sommer; Michael J. Churley; W. Chuck Ramsey - Web page: https://patentgrep.com/patent/US5348587A ## CPC - C23C 16/34: Nitrides {(C23C16/303 takes precedence)} - C23C 16/4401: {Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber} - C23C 16/4405: {Cleaning of reactor or parts inside the reactor by using reactive gases} - 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) ## Abstract A cold wall CVD reactor, particularly one for use in depositing TiN in a TiCl.sub.4 +NH.sub.3 reaction, is provided with a metallic liner insert in partially thermally insulated from the reactor wall which serves as one plasma electrode to form a weak secondary plasma when energized along with a second electrode near the vacuum exhaust port of the reactor. The plasma, in cooperation with radiant lamps provided to heat a wafer substrate onto which the primary CVD film is to be applied, heats the liner and a portion of the space adjacent the reactor walls and susceptor surfaces downstream of the reaction volume to cause the formation of deposits to be of the nature that can be removed by plasma cleaning without opening the reactor volume. Deposits such as TiN.sub.x Cl.sub.y and TiN form at temperatures of approximately 200.degree. C. to 650.degree. C., preferably between 300.degree. C. and 450.degree. C., rather than adduct ammonia salts of TiCl.sub.4, which would tend to form at temperatures of 200.degree. C. or less. ## Claims ### Claim 1 An apparatus for processing semiconductor wafers comprising: a CVD reaction chamber bounded by a sealable cold wall and having a wafer supporting susceptor contained therein, a heater positioned to heat a wafer supported on the susceptor to a primary reaction temperature, a reaction gas inlet, and a gas outlet, the susceptor, inlet and outlet being positioned such that reaction gases from the inlet flow in a path from the inlet, against the susceptor, and downstream to the outlet; a surface liner on the cold wall partially thermally insulated therefrom, along the path downstream from the susceptor, on internal surfaces of the chamber where undesirable particulate contaminants tend to form when unspent reaction gases contact the cold reactor wall; a secondary electrode in the path downstream of the susceptor; an electrical potential source, connected to the secondary electrode, sufficient to form a low energy plasma in gas between the secondary electrode and at least a portion of the reactor surfaces that are in contact with gases flowing downstream of the susceptor to raise the temperature of gas downstream of the susceptor to a temperature above that at which undesirable contaminants will form but below the primary reaction temperature. ### Claim 2 (depends on 1) The apparatus of method of claim 1 wherein: the surface liner is a thin metal insert partially thermally insulated from the cold wall by its limited contact therewith and by the maintenance of the vacuum pressure level within the reactor. ### Claim 3 (depends on 1) The apparatus of claim 1 wherein: the liner is at least in part in contact with the low energy plasma so as to be heated thereby to a temperature above that at which the undesirable contaminants will form but below the primary reaction temperature. ### Claim 4 (depends on 1) The apparatus of claim 1 wherein: the heater includes a source of radiant heat in the vicinity of the susceptor directed to heat a wafer thereon to the primary reaction temperature; and the liner being positioned with respect to the source of radiant heat so as to be at least partially heated by radiant heat therefrom to a temperature above that at which the undesirable contaminants will form but below the primary reaction temperature. ### Claim 5 (depends on 1) The apparatus of claim 1 further comprising: means for supplying TiCl.sub.4 and NH.sub.3 reaction gases to the inlet; means for controlling the heater, pressure within the chamber, and the reaction gas flow to cause the chemical vapor deposition of TiN on a wafer supported on the susceptor by the reaction of 6TiCl.sub.4 +8NH.sub.3 .fwdarw.6TiN+N.sub.2 +24 HCl; and the electrical potential source being operative to form the low energy plasma such that the temperature of the gas downstream of the reaction volume is raised to a temperature of at least approximately 200.degree. C. but the temperature of the wafer. ### Claim 6 (depends on 5) The apparatus of claim 5 wherein: the liner is at least in part in contact with the low energy plasma and thereby heated to at least approximately 250.degree. C. but not more than approximately 450.degree. C. ### Claim 7 (depends on 5) The apparatus of claim 5 wherein: the heater includes a source of radiant heat in the vicinity of the susceptor directed to heat a wafer thereon to the primary reaction temperature; and the liner is positioned with respect to the source so as to be at least partially heated by radiant heat therefrom to a temperature above approximately 200.degree. C. ### Claim 8 (depends on 5) The apparatus of claim 5 further comprising: a NF.sub.3 plasma generator connected to the reactor and operable to clean the reactor with an NF.sub.3 plasma while the reactor is sealed.