PROCESS FOR FORMING LOW RESISTIVITY TITANIUM NITRIDE FILMS

Abstract: A process for forming low resistivity titanium nitride films on a silicon substrate by chemical vapor deposition includes a post-deposition (5) ammonia anneal to provide hydrogen atoms which chemically react with chlorine atoms entrained within the titanium nitride film. The titanium nitride film is deposited by placing the silicon substrate in a reaction chamber, heating the silicon substrate within (10) the reaction chamber, initially passing both TiCl4 gas and NH3 gas into the reaction chamber over the silicon substrate to deposite titanium nitride upon a surface of the silicon substrate, and thereafter discontinuing the flow of TiCl4 gas while continuing to pass NH3 gas (15) into the reaction chamber over the silicon substrate to react with and remove residual chlorine atoms retained by the deposited titanium nitride film.

Description: PROCESS FOR FORMING LOW RESISTIVITY TITANIUM NITRIDE FILMS This application is a continuation-in-part of Application Serial No. 07/746,667, filed August 16, 1991. Background of the Invention The present invention relates generally to semiconductor substrates having thin films of titanium nitride (TiN) deposited thereon by low pressure chemical vapor deposition (LPCVD) methods, , and more particularly, to a process for reducing the chlorine content of such TiN films for lessening the resistivity of such films. Description of the Prior Art It is well known in the semiconductor industry to use thin films of titanium nitride (TiN) as a barrier -metal for semiconductor devices. Such thin films of TiN can be deposited using chemical vapor deposition (CVD) techniques. As a barrier metal, such thin films of TiN may be deposited over semiconductor contact areas prior to formation of aluminum contact layers to prevent the aluminum connection layer from directly contacting the underlying semiconductor SUBSTITUTE SHEET material, which is most typically silicon. Such TiN films provide good step coverage over the surface of the semiconductor substrate, particularly within submicron contacts. Such TiN films also provide low contact resistance to salicide, low leakage, , excellent adhesion to the underlying semiconductor substrate, and high thermal stability. Such TiN films also provide good adhesion for subsequent films of tungsten. In Sherman, "Growth and Properties of LPCVD Titanium Nitride as a Diffusion Barrier for silicon Device Technology," J. Electrochem. Soc. , Vol. ' 137, No. 6, June 1990, a process is described for depositing thin films of TiN upon a silicon substrate in a single-wafer cold wall reactor using a low pressure CVD (LPCVD) process. Accordingly, it is an object of the present invention to provide a process for forming titanium nitride films upon silicon substrates having a decreased sheet resistance. It is still another object of the present invention to provide a process for forming titanium nitride films upon silicon substrates wherein such titanium nitride films have a decreased chlorine content. c, It is yet another object of the present invention to provide such a process which can be performed without substantially altering the flow gases or apparatus commonly used to deposit such titanium nitride films. These and other objects of the present invention will become more apparent to those skilled in the art as the UBSTITUTE SHEET description thereof proceeds. Summary of the Invention Briefly described, and in accordance with the preferred embodiments thereof, the present invention relates to a process for forming low resistivity titanium nitride films on a silicon substrate by chemical vapor deposition, wherein the process includes the steps of placing the silicon substrate in a reaction chamber, heating the silicon substrate within the reaction chamber, initially passing both TiCl 4 gas and NH 3 gas into the reaction chamber over the silicon substrate to deposit titanium nitride upon a surface of the silicon substrate, and thereafter discontinuing the flow of TiCl 4 gas while passing a hydrogen-bearing gas that is reactive with chlorine into the reaction chamber over the silicon substrate to react with and remove residual chlorine atoms retained by the deposited titanium nitride film. The aforementioned hydrogen-bearing gas is preferably NH 3 gas. In the preferred embodimdent of the present invention, the initial flow of NH 3 gas into the reaction chamber is continued over the silicon substrate after the flow of TiC14 gas is discontinued, allowing hydrogen atoms to react with residual chlorine retained by the deposited titanium nitride film at the end of the titanium nitride growth cycle as a post deposition process. The hydrogen atoms react with the chlorine atoms to form gaseous components that leave the titanium nitride film surface. Brief Description of the Drawing UBSTITUTESHEET Fig. 1 is a three-dimensional plot showing sheet resistance of a deposited titanium nitride layer over a range of temperatures and pressures for both a post- deposition argon inert gas anneal and a postdeposition ammonia (NH 3 gas) anneal step. Detailed Description of a Preferred Embodiment In the preferred embodiment of the present invention, titanium nitride films are deposited upon silicon substrates using low pressure chemical vapor deposition (LPCVD) techniques. A silicon wafer is loaded into a reaction chamber, and TiCl 4 gas and NH 3 gas are caused to pass over the silicon wafer. The TiCl 4 gas and NH 3 gas react to deposit a titanium nitride (TiN) film upon the exposed surface of the silicon wafer. However, LPCVD TiN films deposited from TiCl 4 gas and NH 3 gas incorporate a large amount of chlorine in the film. This chlorine has been found to be concentrated at the grain boundaries and film interfaces. The use of NH 3 gas to react and strip off the remaining unbound chlorine has been found by Applicants to be effective in lowering the chlorine film content. Applicants believe that the hydrogen gas reacts with the chlorine atoms to form HC1 gas that is carried off away from the titanium nitride film. The present process of using NH 3 gas to react and strip off the remaining unbound chlorine is preferably performed insitu at the end of the TiN growth cycle as a post deposition process. The use of NH 3 gas differs from simple diffusion mechanisms, such as the use of inert gases SUBSTITUTESHEET like argon or nitrogen, which fail to strip off all the available chlorine. For example, in Fig. 1, a plot is shown indicating sheet resistance of the deposited titanium nitride layer over a range of temperatures and pressures for both a post-deposition argon anneal and a postdeposition ammonia (NH 3 gas) anneal step. As shown in Fig. 1, the sheet resistance is continuously lower when the ammonia anneal step is performed as compared with the argon anneal step. Applicants believe that standard post deposition annealing treatments in inert environments merely activate chlorine diffusion through the film; however, this diffusion mechanism does not reactively separate the bound chlorine from the grain boundaries. The use of an insitu ammonia anneal step accomplishes two objectives. First, the chloride content of the titanium nitride film can be reduced from approximately 2% to 0.7%, which allows the film resistivity to' be reduced. Secondly, the sheet resistance uniformity is improved from approximately 8% to 4%. In practicing the present invention, a single- wafer LPCVD TiN reactor is preferably used. The temperature range within the reactor during the anneal step may be from 600 degrees Centigrade to 700 degrees Centigrade, with the temperature range of 650-680 degrees Centigrade being preferred. The preferred pressure range within the reactor was 115 mTorr. to 300 mtorr. Preferred gas flow ranges are 10 seem for TiCl 4 gas and 100 seem, for the NH 3 gas, wherein the term "seem" designates standard cubic centimeters per minute. An Argon gas carrier having a flow rate of 30 seem is added to the TiCl 4 gas flow path prior to injection into the reactor to balance the flow through the gas injector manifold of the reaction chamber. The TiCl 4 gas and the NH 3 gas are injected through two different sets of injector ports to avoid mixing of such gases within the gas manifold prior to injection into the reaction chamber. In the preferred embodiment, the deposition of the TiN film was conducted for 60 seconds, followed by an ammonia anneal for 60 seconds. The longer the anneal period, the better the resistivity enhancement. Of course, the period for the ammonia anneal is partly dependent upon the temperature. For anneal temperatures within the range of 650-680 degrees Centigrade, the anneal time period varies between 30-90 seconds. At lower temperatures, a longer anneal period is needed to yield the same resistivity. Most often, the deposition step and anneal step are performed at same temperature, though the reaction chamber can be quickly raised after the deposition step to lower the anneal time to 30-45 seconds. It had been theorized by the applicants that merely increasing the percentage of NH 3 gas relative to TiCl 4 gas during the deposition phase might reduce the tendency for chlorine atoms to be retained within the titanium nitride film. However, experiments conducted by the applicants failed to show this to be true. By reducing the titanium nitride film resistivity, one decreases series resistance between the underlying silicon and the overlying metal connection network. Also, by making the sheet resistance of the titanium nitride film more uniform, one increases the yield of working circuits on a semiconductor wafer, thereby lowering the production cost for such circuits. If desired, the ammonia anneal post deposition step may be carried out in a process chamber different than the LPCVD reaction process chamber in which the titanium nitride film deposition step is carried out. This approach may be useful when the film deposition step and the post deposition anneal step are carried out in separate process chambers of a cluster tool having a centrally located substrate transport compartment which sequentially transfers the substrate in a controlled oxygen-free vacuum environment to a film deposition LPCVD process chamber, thereafter from the film deposition LPCVD chamber to the post deposition ammonia anneal process chamber, and subsequently from the post deposition ammonia anneal process chamber for further processing, storage in a cassette or the like. The temperature in the separate post anneal process chamber could be the same temperature as in the film deposition LPCVD chamber, or a different temperature, either higher or lower. Alternatively, the substrate could be removed from the LPCVD process chamber after the film formation step and transported under normal uncontrolled oxygen-containing air atmospheric conditions to a standalone post anneal process chamber which is physically separate from the LPCVD chamber SUBSTITUTESHEET and not interconnected therewith via an oxygen-free controlled atmosphere and/or vacuum substrate transport compartment. As with the cluster tool configuration des¬ cribed above, , the temperature in the standalone post anneal chamber may be different than that in the film forming LPCVD chamber, either higher or lower. WE CLAIM:

Claims: 1. A process for forming low resistivity titanium nitride films on a silicon substrate by chemical vapor deposition, said process comprising in combination the steps of: a. placing the silicon substrate in a reaction chamber; b. heating the silicon substrate within the reaction chamber; c. passing both TiCl 4 gas into the reaction chamber over the silicon substrate to deposit titanium nitride upon a surface of the silicon substrate; d. following step c. , discontinuing the flow of TiCl 4 gas while continuing the flow of NH 3 gas into the reaction chamber over the silicon substrate to react with residual chlorine retained by the deposited titanium nitride film. SUBSTITUTESHEET 2. The process of claim 1 wherein the temperature within the chamber during steps c. and d. is substantially the same. 3. The process of claim 1 wherein the temperature within the chamber during steps c. and d. is within the approximate range of 600-700 degrees Centigrade. SUBSTITUTESHEET 4. The process of claim 1 wherein the temperature within said reaction chamber during step d. lies within the approximate range of 650-680 degress Centigrade. 5. The process of claim 1 wherein the pressure within said reaction chamber during step d. lies within the approximate range of 115 mTorr. and 300 mTorr. 6. The process of claim 1 wherein the flow of NH 3 gas into the reaction chamber over the silicon substrate is continued for approximately 30 seconds to 90 seconds after the flow of TiCl 4 gas is discontinued. SUBSTITUTESHEET 7. The process for forming low resistivity titanium nitride films on a silicon substrate by chemical vapor deposition, said process comprising in combination the steps of: a. place the silicon substrate in a reaction chamber; b. heating the silicon substrate within the reaction chamber; c. passing both TiCl 4 gas and NH 3 gas into the reaction chamber over the silicon substrate to deposit titanium nitride upon a surface of the silicon substrate; d. following step c, discontinuing the flow of TiCl 4 gas while passing a hydrogen-bearing gas that is reactive with chlorine into the reaction chamber over the silicon substrate to react with residual chlorine retained by the deposited titanium nitride film. SUBSTITUTE T 8. The process recited by claim 7 wherein said hydrogen-bearing gas is NH 3 gas. SUBSTITUTESHEET 9. A process for forming low resistivity titanium nitride films on a silicon substrate by chemical vapor deposition, said process comprising in combination the steps of: a. placing the silicon substrate in a reaction chamber; b. heating the silicon substrate within the reaction chamber; c. depositing a titanium nitride film upon the silicon substrate by passing thereover TiCl 4 gas and at least one other gas reactive therewith; d. discontinuing the flow of TiCl 4 gas; and e. passing NH 3 gas into the reaction chamber over the silicon substrate to react with residual chlorine retained by the deposited titanium nitride film. SUBSTITUTESHEET 10. The process of claim 9 wherein the temperature within said reaction chamber during step e. lies within the approximate range of 600-700 degrees Centigrade. 11. The process of-claim 9 wherein the pressure within said reaction chamber during step e. lies within the approximate range of 115 mTorr. to 300 mTorr. 12. The process recited by claim 9 wherein NH 3 gas is passed into the reaction chamber over the silicon substrate in step e. for approximately 30 seconds to 90 seconds after the flow of TiCl 4 gas is discontinued. SUBSTITUTE SHEET 13. The process of claim 9 wherein the temperature within the reaction chamber during step e. lies within the approximate range of 650-680 degrees Centigrade. TITUTESHEET 14. A process for forming low resistivity titanium nitride films on a silicon substrate by chemical vapor deposition, said process comprising in combination the steps of: a. placing the silicon substrate in a reaction chamber; b. passing NH 3 gas over the silicon substrate following deposition of the titanium nitride film to react with residual chlorine retained by the deposited titanium nitride film. T T ET 15. The process of claim 14 wherein steps a. and b. occur in the same process chamber without removal of the substrate therefrom between the steps. 16. The process of claim 14 wherein steps a. and b. occur in different process chambers and the substrate is transported between the different process chambers through a.-transport chamber maintained at a vacuum which interconnects the different process chambers. 17. The process of claim 16 wherein the transport chamber is maintained substantially oxygen-free during transport of the substrate between the different process chambers. SUBSTITUTESHEET 18. The process of claim 14 wherein steps a. and b. occur in different process chambers and the substrate is transported between the different process chambers in an air atmosphere. SUBSTITUTESHEET [received by the International Bureau on 8 February 1993 (08.02.93); original claims 1,7 and 9 amended; other claims unchanged (6 pages)] (1) A process for forming low resistivity titanium nitride films on a silicon substrate by chemical vapor deposition, said process comprising in combination the steps of: a. placing the silicon substrate in a reaction chamber; b. heating the silicon substrate within the reaction chamber; c. passing both TiCl. gas and NH3 gas into the reaction chamber over the silicon substrate to deposit titanium nitride upon a surface of the silicon substrate, said deposited film containing chlorine and having a sheet resistivity; d. following step c. , discontinuing the ■ flow of TiCl4 gas while continuing the flow of NH3 gas into the reaction chamber over the silicon substrate to react with residual chlorine retained by the deposited titanium nitride film, thereby lowering the chlorine content of the film and reducing the film sheet resistivity. (2) The process of claim 1 wherein the temperature within the chamber during steps c. and d. is substantially the same. (3) The process of claim 1 wherein the temperature within the chamber during step d. is within the approximate range of 600-700 degrees Centigrade. (4) The process of claim 1 wherein the temperature within said reaction chamber during step d. lies within the approximate range of 650-680 degrees Centigrade. (5) The process of claim 1 wherein the pressure within said reaction chamber during step d. lies within the approximate range of 115 mTorr. and 300 mTorr. (6) The process of claim 1 wherein the flow of NH3 gas into the reaction chamber over the silicon substrate is continued for approximately 30 seconds to 90 seconds after the flow of TiCl4 ,gas is discontinued. (7) A process for forming low resistivity titanium nitride films on a silicon substrate by chemical vapor deposition, said process comprising in combination the steps of: a. placing the silicon substrate in a reaction chamber; b. heating the silicon substrate within the reaction chamber; c. passing both iCl4 gas and NH3 gas into the reaction chamber over the silicon substrate to deposit titanium nitride upon a surface of the silicon substrate, said deposited film containing chlorine and having a sheet resistivity; d. following step c. , discontinuing the flow of TiCl4 gas while passing a hydrogen-bearing gas that is reactive with chlorine into the reaction chamber over the silicon substrate to react with residual chlorine retained by the deposited titanium nitride film, thereby lowering the chlorine content of the film and reducing the film sheet resistivity. (8) The process recited by claim 7 wherein said hydrogen-bearing gas is NH3 gas. (9) A process for forming low resistivity titanium nitride films on a silicon substrate by chemical vapor deposition, said process comprising in combination the steps of: a. placing the silicon substrate in a reaction chamber; b. heating the silicon substrate within the reaction chamber; c. depositing a titanium nitride film upon the silicon substrate by passing thereover TiCl4 gas and at lest one other gas reactive therewith, said deposited film containing chlorine and having a sheet resistivity; d. discontinuing the flow of TiCl4 gas; and e. passing NH 3 gas into the reaction chamber over the silicon substrate to react with residual chlorine retained by the deposited titanium nitride film, thereby lowering the chlorine content of the film and reducing the film sheet resistivity. (10) The process of claim 9 wherein the temperature within said reaction chamber during step e. lies within the approximate range of 600-700 degrees Centigrade. (11) The process of claim 9 wherein the pressure within said reaction chamber during step e. lies within the approximate range of 115 mTorr. to 300 mTorr. (12) The process recited by claim 9 wherein NH3 gas is passed into the reaction chamber over the silicon substrate in step e. for approximately 30 seconds to 90 seconds after the flow of TiCl4 gas is discontinued. (13) The process of claim 9 wherein the temperature within the reaction chamber during step e. lies within the approximate range of 650-680 degrees Centigrade. (14) A process for forming low resistivity titanium nitride films on a silicon substrate by chemical vapor deposition, said process comprising in combination the steps of: a. placing the silicon substrate in a reaction chamber; b. passing NH3 gas over the silicon substrate following deposition of the titanium nitride film to react with residual chlorine retained by the deposited titanium nitride film. (15) The process of claim 14 wherein steps a. and b. occur in the same process chamber without removal of the substrate therefrom between the steps. (16) The process of claim 14 wherein steps a. and b. occur in different process chambers and the substrate is transported between the different process chambers through a transport chamber maintained at a vacuum which interconnects the different process chambers. (17) The process of claim 16 wherein the transport chamber is maintained substantially oxygen-free during transport of the substrate between the different process chambers. (18) The process of claim 14 wherein steps a. and b. occur in different process chambers and the substrate is transported between the different process chambers in an air atmosphere.

Inventors: CHURLEY MICHAEL J, EICHMAN ERIC C, SOMMER BRUCE A, CHURLEY, MICHAEL, J., EICHMAN, ERIC, C., SOMMER, BRUCE, A.
Applicants: MATERIALS RESEARCH CORP, MATERIALS RESEARCH CORPORATION
Application year: 1992
Main classification: H01L21
IPC codes: C23C16, H01L21