Method of nucleating tungsten on titanium nitride by CVD without silane

• US 5,342,652 A
• Filed: 06/15/1992
• Issued: 08/30/1994
• Est. Priority Date: 06/15/1992
• Status: Expired due to Term

• Current Assignee: Tokyo Electron Limited
• Original Assignee: Materials Research Corporation (Linde Plc)
• Inventors: Srinivas, Damodaran, Foster, Robert F.
• Primary Examiner(s): PIANALTO, BERNARD D
• Application Number:
  US07/898,565
• Time in Patent Office: 806 Days
• Field of Search: 427/250, 427/253, 427/255, 427/255.1, 427/255.7, 427/464, 427/419.7
• US Class Current: 427/253
• CPC Class Codes: C23C 16/0218 in a reactive atmosphere C23C16/0227 takes precedence
• CPC Class Codes: C23C 16/04 Coating on selected surface areas, e.g. using masks
• CPC Class Codes: C23C 16/14 Deposition of only one other metal element
• CPC Class Codes: H01L 21/28556 by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence

Abstract

Nucleation of a refractory metal such as tungsten is initiated on a substrate of TiN without the use of silane by introducing hydrogen into a CVD reactor before the introduction of the reactant gas containing the metal, brought to reaction temperature and to reaction pressure. The process is most useful for CVD of tungsten onto patterned TiN coated silicon semiconductor wafers. Alternatively, hydrogen is introduced in a mixture with the metal containing gas, such as WF₆, and maintained at subreaction pressure, of for example 100 mTorr, until the substrate is stabilized at a reaction temperature of approximately 400° C. or higher, to cause the dissociation of hydrogen on the wafer surface, then elevated to a relatively high reaction pressure of, for example, 60 Torr at which nucleation is achieved. Also, the reduction reaction that deposits the tungsten film proceeds without the need for a two step nucleation-deposition process.

Claims

1. A method of nucleating tungsten in a tungsten CVD process performed in a vacuum chamber without the use of silane to deposit elemental tungsten onto a substrate, the method comprising the steps of:

injecting hydrogen into the chamber and bringing the chamber to a pressure and temperature sufficient to produce a hydrogen dissociation reaction at the substrate before the introduction of WF₆ into the chamber; and

then injecting WF₆ into the chamber in a ratio with H₂ and at a pressure and temperature to produce a reduction reaction resulting in tungsten deposition onto the substrate.

2. The method of claim 1 wherein:

the hydrogen is injected into the chamber and brought to a pressure and temperature sufficient to produce a WF₆ reduction reaction before the introduction of WF₆ into the chamber.

3. The method of claim 1 wherein:

the reaction pressure is above approximately 3 Torr.

4. The method of claim 1 wherein:

the reaction pressure is above approximately 50 Torr.

5. The method of claim 1 wherein:

the reaction temperature is above approximately 400°

C.

6. The method of claim 1 wherein:

the substrate has a surface film thereon formed of TiN.

7. A method of nucleating tungsten in a tungsten CVD process performed in a vacuum chamber without the use of silane to deposit elemental tungsten onto a substrate, the method comprising the steps of:

injecting a gas mixture of hydrogen and WF₆ into the chamber and maintaining the chamber at a subreaction pressure below that for a WF₆ reduction reaction at the temperature of the substrate; and

before increasing the pressure from the subreaction pressure, maintaining the temperature of the substrate at least at that for the dissociation of hydrogen; and

then increasing the pressure in the chamber to a WF₆ reduction reaction pressure.

8. The method of claim 7 wherein:

the subreaction pressure is below approximately 1 Torr.

9. The method of claim 7 wherein:

the reaction pressure is above approximately 3 Torr.

10. The method of claim 7 wherein:

the reaction pressure is above approximately 50 Torr.

11. The method of claim 7 wherein:

the maintained temperature is above approximately 400°

C.

12. The method of claim 7 wherein:

the substrate has a surface film thereon formed of TiN.

13. A method of nucleating tungsten in a CVD process performed by reduction of WF₆ in a vacuum chamber without the use of silane to deposit a metal onto a substrate, the method comprising the steps of:

injecting a gas including hydrogen into the chamber;

injecting a gas including WF₆ into the chamber with or following the introduction of hydrogen into the chamber;

elevating the pressure of the gas within the chamber from a subreaction pressure to at least a minimum reaction pressure;

elevating the temperature of the substrate and the gases within the chamber to at least a minimum reaction temperature before WF₆ gas within the chamber is raised to the minimum reaction pressure.

14. The method of claim 13 wherein:

the substrate has a surface formed of material selected from the group consisting of CVD TiN, reactively sputtered TiN, or rapid thermal process formed TiN.

15. The method of claim 13 wherein:

the reaction pressure is above approximately 50 Torr.

16. The method of claim 13 wherein:

the reaction temperature is above approximately 400°

C.

17. The method of claim 13 wherein:

WF₆ gas within the reaction chamber, prior to the elevation of the substrate temperature to the reaction temperature, is maintained at a pressure of not more than approximately 1 Torr.

18. The method of claim 13 wherein:

from prior to introduction of the H₂ and WF₆ gases until after completion of a tungsten deposition process on the wafer, the wafer is rotated about its center at a speed sufficient to thin a boundary layer across the wafer and to facilitate the transfer of mass between the gases and the wafer.

19. The method of claim 13 further comprising the preliminary steps of:

depositing a TiN film on the wafer in a first vacuum processing chamber of a wafer processing apparatus;

transferring the wafer having the TiN film thereon to a second vacuum processing chamber of a wafer processing apparatus; and

performing the gas injecting steps, pressure elevating step and temperature elevating step on the wafer in the second vacuum processing chamber.

20. The method of claim 19 wherein:

the first and second chambers are connected in the same wafer processing apparatus having a wafer transfer path therebetween containing inert gas maintained at a vacuum pressure level;

the step of transferring the wafer is performed with the wafer maintained in the inert gas at the vacuum pressure level while from the first to the second chamber without exposure of the wafer to an external environment.