Method of forming a metal film for electrode

• US 7,829,144 B2
• Filed: 01/11/2005
• Issued: 11/09/2010
• Est. Priority Date: 11/05/1997
• Status: Expired due to Fees

• Current Assignee: Tokyo Electron Limited
• Original Assignee: Tokyo Electron Limited
• Inventors: Matsuse, Kimihiro, Otsuki, Hayashi
• Primary Examiner(s): Meeks; Timothy
• Assistant Examiner(s): Gambetta; Kelly M
• Application Number:
  US11/032,060
• Publication Number:
  US 20050191803A1
• Time in Patent Office: 2,128 Days
• Field of Search: 427/248.1
• US Class Current: 427/248.1
• CPC Class Codes: H01L 21/28061 the conductor comprising a metal or metal silicide formed by deposition, e.g. sputter deposition, i.e. without a silicidation reaction H01L21/28052 takes precedence
• 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
• CPC Class Codes: H01L 21/28568 the conductive layers comprising transition metals H01L21/28518 takes precedence
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76877 Filling of holes, grooves or trenches, e.g. vias, with conductive material
• CPC Class Codes: H01L 23/53238 Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
• CPC Class Codes: H01L 29/4941 with a barrier layer between the silicon and the metal or metal silicide upper layer, e.g. Silicide/TiN/Polysilicon
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

A method of forming a refractory metal film doped with III or V group elements. The first process gas is supplied from a first gas source through a first gas introducing member to and through a gas supply mechanism toward a substrate within a processing vessel. The second process gas is supplied from a second gas source through a second gas introducing member to and through the gas supply mechanism toward the substrate within the processing vessel. The processing vessel is purged by evacuating the processing vessel by an evacuating mechanism, while supplying the inert gas from a third source through a third gas introducing member to and through the gas supply mechanism into the processing vessel. The supplying the first process gas and the supplying the second process gas are repeated with the supplying the purging gas being carried out between supplying the first and second gases performed so that residual gas present in the processing vessel after performing the supplying of the first and second process gases is reduced to a level of 1 to 30% based on the entire capacity of the processing vessel.

Claims

1. A method of forming a refractory metal film doped with at least one of III or V group elements, using an apparatus comprising (i) a processing vessel, (ii) a supporting member which is provided in the processing vessel and supports a substrate, (iii) a heater which heats the substrate supported by the supporting member, (iv) a gas supply mechanism for supplying gases towards the substrate in the processing vessel, (v) an evacuating mechanism for evacuating the processing vessel, (vi) a first gas source for storing a first gas including refractory metallic atoms, (vii) a second gas source for storing a second gas including at least one of III or V group elements, (viii) a third gas source for storing an inert gas, and (ix) first to third gas introducing pipes for selective fluid communication between the first to third gas sources and the gas supply mechanism,

the method comprising:

supplying the first gas from the first gas source through the first gas introducing pipe and through a first port inside the gas supply mechanism toward the substrate within the processing vessel;

supplying the second gas from the second gas source through the second gas introducing pipe and through a second port inside the gas supply mechanism toward the substrate within the processing vessel, wherein the first and second ports in the gas supply mechanism comprise separate gas spray ports dispersing respectively the first and second gases from the gas supply mechanism from different ports;

purging the processing vessel by evacuating the processing vessel by the evacuating mechanism, while supplying the inert gas from the third gas source through the third gas introducing pipe and through the gas supply mechanism into the processing vessel, while the processing vessel is evacuated by the evacuating mechanism to exhaust the inert gas from the processing vessel; and

repeating the supplying the first gas and the supplying the second gas by opening a first valve for introducing the first gas into the processing vessel and closing a second valve for introducing the second gas into the processing vessel, and by closing the first valve for introducing the first gas into the processing vessel and opening the second valve for introducing the second gas into the processing vessel,

wherein the supplying the first gas and the supplying the second gas are repeated with the purging the processing vessel being carried out between the supplying the first and second gases so that residual gas present in the processing vessel after performing the supplying the first and second gases is reduced to a level of 1 to 30% based on an entire capacity of the processing vessel, and

wherein said first and second gasses temporally exist in the processing vessel at different times.

2. The method according to claim 1, wherein said refractory metal film is a W film which is formed by alternately repeating a plurality of times the supplying the first and second gases, the first gas including a WF₆ gas, and the second gas including boron.

3. The method according to claim 1, wherein said refractory metal film is a Wsi_x film which is formed by alternately repeating a plurality of times the supplying the first and second gases, the first gas including a WF₆ gas, the second gas including boron, and at least one of the first and second gases including a silane group gas.

4. The method according to claim 1, wherein a silane group gas is supplied into the processing vessel before initially supplying the first gas toward the substrate.

5. The method according to claim 4, further comprising:

forming a metal layer on the refractory metal film.

6. The method according to claim 5, wherein the metal layer is a W layer having a thickness greater than a thickness of the refractory metal film.

7. The method according to claim 4, further comprising:

supplying a silane group gas between the formations of the refractory metal film and metal layer.

8. The method according to claim 1, wherein said refractory metal film is a WSI_x film which is formed by alternately repeating the supplying the first and second gases a plurality of times, the first gas including a WF₆ gas and an SiH₄ gas and the second gas including boron.

9. The method according to claim 1, wherein said refractory metal film is a W film which is formed by alternately repeating the supplying the first and second gases a plurality of times, the first gas including a B₂H₆ gas and a WF₆ gas and the second gas including boron.

10. The method according to claim 9, wherein the second gas is a B₂H₆ gas supplied before the supplying the first gas.

11. The method according to claim 1, wherein said refractory metal film is a W film which is formed by alternately repeating the supplying the first and second gases a plurality of times, the first gas including a WF₆ gas and the second gas including boron.

12. The method according to claim 1, wherein the supporting member immovably supports the substrate.

13. A method of forming a nuclear layer formed by a refractory metal film doped with at least one of III or V group elements, using an apparatus comprising (i) a cylindrical processing vessel having a longitudinal axis, (ii) a supporting member which is provided in the processing vessel and supports a plurality of substrates along the longitudinal axis in an interval, (iii) a heater which is provided around the substrates and heats the substrates supported by the supporting member, (iv) a gas supply mechanism having at least one gas spray port provided on one side of the processing vessel, for spraying gases into the processing vessel, (v) an evacuating mechanism for evacuating the processing vessel so that the gases sprayed into the processing vessel flow from said one side to the other side of the processing vessel, (vi) a first gas source for storing a first gas including refractory metallic atoms, (vii) a second gas source for storing a second gas including at least one of III or V group elements, (viii) a third gas source for storing an inert gas, and (ix) first to third gas introducing pipes for selective fluid communication between the first to third gas sources and the gas supply mechanism,

the method comprising:

supplying the first gas from the first gas source through the first gas introducing pipe and through the gas supply mechanism toward the substrate within the processing vessel;

supplying the second gas from the second gas source through the second gas introducing pipe and through the gas supply mechanism toward and across the substrate within the processing vessel, wherein the gases sprayed into the processing vessel flow from said one side to the other side of the processing vessel;

purging the processing vessel by evacuating the processing vessel by the evacuating mechanism, while supplying the inert gas from the third source through the third gas introducing pipe and through the gas supply mechanism into the processing vessel, while the processing vessel is evacuated by the evacuating mechanism to exhaust the inert gas from the processing vessel; and

repeating the supplying the first gas and the supplying the second gas by opening a first valve for introducing the first gas into the processing vessel and closing a second valve for introducing the second gas into the processing vessel, and by closing the first valve for introducing the first gas into the processing vessel and opening the second valve for introducing the second gas into the processing vessel,

wherein the supplying the first process gas and the supplying the second gas are repeated with the purging the processing vessel being carried out between the supplying the first and second gases to form the refractory metal film by atomic layer deposition, so that residual gas present in the processing vessel after performing the supplying the first and second gases is reduced to a level of 1 to 30% based on an entire capacity of the processing vessel, and

wherein said first and second gasses temporally exist in the processing vessel at different times.

14. The method according to claim 13, wherein said refractory metal film is a WSI_x film which is formed by alternately repeating the supplying the first and second gases a plurality of times, the first gas including a SiH₄ gas and a WF₆ gas and the second gas including boron.

15. The method according to claim 14, wherein the second gas is supplied before the supplying of the first gas.

16. The method according to claim 13, wherein said refractory metal film is a W film which is formed by alternately repeating the supplying the first and second gases a plurality of times, the first gas including a WF₆ gas and the second gas including boron.

17. The method according to claim 13, wherein said metal film is a W film which is formed by alternately repeating the supplying the first and second gases a plurality of times, the first gas including a WF₆ gas and the second gas including boron.

18. The method according to claim 13, wherein the supporting member immovably supports the substrate.

19. A method of forming a refractory metal film doped with at least one of III or V group elements, using an apparatus comprising (i) a processing vessel, (ii) a supporting member which is provided in the processing vessel and supports a substrate, (iii) a heater which heats the substrate supported by the supporting member, (iv) first and second gas supply mechanisms for supplying gases into the processing vessel, the first gas supplying mechanism having at least one first gas supply port provided on one side of the processing vessel, the second gas supply mechanism having at least one second gas supply port provided on the other side of the processing vessel, and the substrate being positioned between the first and second gas supply ports, (v) first and second evacuating mechanisms for evacuating the processing vessel, the first evacuating mechanism having at least one first gas evacuating port provided on the other side of the processing vessel, the second evacuating mechanism having at least one second evacuating port provided on said one side, and the substrate being positioned between the first and second evacuating ports, (vi) a switching mechanism for intermittently switching between a gas flow from the first gas supply port to the first exhaust port and a gas flow from the second gas supply port to the second exhaust port, (vii) a first gas source for storing a first gas including refractory metallic atoms, (viii) a second gas source for storing a second gas including at least one of III or V group elements, (ix) a third gas source for storing an inert gas, and (x) first to third gas introducing pipes for selective fluid communication between the first to third gas sources and the first and second gas supply mechanisms,

the method comprising:

supplying the first gas from the first gas source through the first gas introducing pipe and through the first gas supply mechanism in a first direction toward and across the substrate within the processing vessel;

supplying the second gas from the second gas source through the second gas introducing pipe and through the second gas supply mechanism in a second direction toward and across the substrate within the processing vessel, wherein the first and second directions result in the gases sprayed into the processing vessel flowing from said one side to the other side of the processing vessel;

purging the processing vessel by evacuating the processing vessel by the evacuating mechanisms, while supplying the inert gas from the third source through the third gas introducing pipe and through at least one of the first and second gas supply mechanisms into the processing vessel, while the processing vessel is evacuated by the evacuating mechanisms to exhaust the inert gas from the processing vessel; and

repeating the supplying the first gas and the supplying the second gas by opening a first valve for introducing the first gas into the processing vessel and closing a second valve for introducing the second gas into the processing vessel, and by closing the first valve for introducing the first gas into the processing vessel and opening the second valve for introducing the second gas into the processing vessel,

wherein the supplying the first gas and the supplying the second gas are repeated with the purging the processing vessel being carried out between the supplying the first and second gases to form the refractory metal film by atomic layer deposition, so that residual gas present in the processing vessel after performing the supplying the first and second gases is reduced to a level of 1 to 30% based on an entire capacity of the processing vessel, and

wherein said first and second gasses temporally exist in the processing vessel at different times.

20. The method according to claim 19, further comprising:

forming a metal layer on the refractory metal film,

wherein the metal layer is a W layer having a thickness greater than a thickness of the refractory metal film.

21. The method according to claim 19, wherein the supporting member immovably supports the substrate.