WO1993004214A1 - Process for forming low resistivity titanium nitride films - Google Patents

Process for forming low resistivity titanium nitride films Download PDF

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Publication number
WO1993004214A1
WO1993004214A1 PCT/US1992/006847 US9206847W WO9304214A1 WO 1993004214 A1 WO1993004214 A1 WO 1993004214A1 US 9206847 W US9206847 W US 9206847W WO 9304214 A1 WO9304214 A1 WO 9304214A1
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Prior art keywords
silicon substrate
gas
reaction chamber
titanium nitride
steps
Prior art date
Application number
PCT/US1992/006847
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French (fr)
Inventor
Eric C. Eichman
Bruce A. Sommer
Michael J. Churley
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Materials Research Corporation
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Filing date
Publication date
Priority claimed from US07/746,667 external-priority patent/US5279857A/en
Application filed by Materials Research Corporation filed Critical Materials Research Corporation
Priority to JP50446793A priority Critical patent/JP3315116B2/en
Priority to EP92918548A priority patent/EP0599991B1/en
Priority to KR1019940700432A priority patent/KR100250586B1/en
Priority to DE69206808T priority patent/DE69206808T2/en
Publication of WO1993004214A1 publication Critical patent/WO1993004214A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides

Definitions

  • 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.
  • TiN titanium nitride
  • LPCVD low pressure chemical vapor deposition
  • TiN titanium nitride
  • CVD chemical vapor deposition
  • 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.
  • 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.
  • 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.
  • 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.
  • titanium nitride films are deposited upon silicon substrates using low pressure chemical vapor deposition (LPCVD) techniques.
  • LPCVD low pressure chemical vapor deposition
  • 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.
  • TiN titanium nitride
  • 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 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.
  • 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.
  • the sheet resistance is continuously lower when the ammonia anneal step is performed as compared with the argon anneal step.
  • 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.
  • 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.
  • the sheet resistance uniformity is improved from approximately 8% to 4%.
  • 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.
  • the deposition of the TiN film was conducted for 60 seconds, followed by an ammonia anneal for 60 seconds.
  • the period for the ammonia anneal is partly dependent upon the temperature.
  • the anneal time period varies between 30-90 seconds. At lower temperatures, a longer anneal period is needed to yield the same resistivity.
  • 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.
  • 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.
  • 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

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Electrodes Of Semiconductors (AREA)

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 TiCl4gas and NH3 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 TiCl4 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 NH3 gas. In the preferred embodimdent of the present invention, the initial flow of NH3 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 (NH3 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 TiCl4 gas and NH3 gas are caused to pass over the silicon wafer. The TiCl4 gas and NH3 gas react to deposit a titanium nitride (TiN) film upon the exposed surface of the silicon wafer. However, LPCVD TiN films deposited from TiCl4 gas and NH3 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 NH3 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 NH3 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 NH3 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 (NH3 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 TiCl4 gas and 100 seem, for the NH3 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 TiCl4 gas flow path prior to injection into the reactor to balance the flow through the gas injector manifold of the reaction chamber. The TiCl4 gas and the NH3 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 NH3 gas relative to TiCl4 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 TiCl4 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 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.
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 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.
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 TiCl4 gas and NH3 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 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.
SUBSTITUTE T
8. The process recited by claim 7 wherein said hydrogen-bearing gas is NH3 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 TiCl4 gas and at least one other gas reactive therewith; d. discontinuing the flow of TiCl4 gas; and e. passing NH3 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 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.
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 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.
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 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.
(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.
PCT/US1992/006847 1991-08-16 1992-08-13 Process for forming low resistivity titanium nitride films WO1993004214A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP50446793A JP3315116B2 (en) 1991-08-16 1992-08-13 Method for producing low resistivity titanium nitride film
EP92918548A EP0599991B1 (en) 1991-08-16 1992-08-13 Process for forming low resistivity titanium nitride films
KR1019940700432A KR100250586B1 (en) 1991-08-16 1992-08-13 Process for forming low resistivity titanium nitride films
DE69206808T DE69206808T2 (en) 1991-08-16 1992-08-13 METHOD FOR PRODUCING TITANIUM NITRIDE FILMS WITH LOW SPECIFIC RESISTANCE

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US746,667 1991-08-16
US07/746,667 US5279857A (en) 1991-08-16 1991-08-16 Process for forming low resistivity titanium nitride films
US07/833,023 US5308655A (en) 1991-08-16 1992-02-10 Processing for forming low resistivity titanium nitride films
US833,023 1992-02-10

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CA (1) CA2114716A1 (en)
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WO1996028586A1 (en) * 1995-03-10 1996-09-19 Materials Research Corporation Plasma enhanced chemical vapor deposition of titanium nitride using ammonia
US6051281A (en) * 1996-10-01 2000-04-18 Tokyo Electron Limited Method of forming a titanium film and a barrier metal film on a surface of a substrate through lamination
US6537621B1 (en) 1996-10-01 2003-03-25 Tokyo Electron Limited Method of forming a titanium film and a barrier film on a surface of a substrate through lamination
DE19600946B4 (en) * 1995-03-28 2005-02-10 Hyundai Electronics Industries Co., Ltd., Ichon A method of improving the quality of a titanium nitride layer containing carbon and oxygen
DE19608208B4 (en) * 1995-03-04 2006-02-23 Magnachip Semiconductor, Ltd. Process for the preparation of metal interconnects in semiconductor devices

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US5308655A (en) 1994-05-03
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