Method of forming a barrier film and method of forming wiring structure and electrodes of semiconductor device having a barrier film

• US 6,861,356 B2
• Filed: 08/22/2002
• Issued: 03/01/2005
• Est. Priority Date: 11/05/1997
• Status: Expired due to Fees

• Current Assignee: Tokyo Electron Limited
• Original Assignee: Tokyo Electron Limited
• Inventors: Otsuki, Hayashi, Matsuse, Kimihiro
• Primary Examiner(s): QUACH, TUAN N
• Application Number:
  US10/225,228
• Publication Number:
  US 20020197856A1
• Time in Patent Office: 922 Days
• Field of Search: 438/627, 438/643, 438/648, 438/653, 438/656, 438/680, 438/681, 438/683, 438/685
• US Class Current: 438/653
• 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

There is provided a method of forming a barrier metal which is designed to be interposed between a metal layer and an insulating layer, both constituting a multi-layered structure of semiconductor device, the method comprising the steps of positioning a substrate having the insulating layer formed thereon at a predetermined position inside a processing vessel forming a processing space, and alternately introducing a gas containing a refractory metallic atom, a gas containing Si atom and a gas containing N atom into the processing vessel under a predetermined processing pressure, thereby allowing a refractory metal nitride or a refractory metal silicon nitride to be deposited on the insulating layer by way of atomic layer deposition.

Claims

1. A method of forming a film with ALD using a chemical vapor deposition apparatus comprising (i) a processing vessel, (ii) a mounting member which is provided in the processing vessel and supports a substrate thereon, (iii) heating means which heat the substrate supported by the mounting member, (iv) gas supply means having a plurality of gas spray ports for spraying gas onto the substrate in the process vessel, (v) evacuating means for evacuating the gas in the processing vessel so that the gas sprayed onto the substrate flows downwardly, (vi) a first gas source for storing a first process gas including refractory metallic atoms, (vii) a second gas source for storing a second process gas including a reducing gas, (viii) a third gas source for storing a third process gas including N, (ix) a fourth gas source for storing an inert gas, (x) a first gas introducing pipe which connects the first gas source to the gas supply means, and (xi) a second gas introducing pipe which connects the second gas source to the gas supply means, at least one of the first and second gas introducing pipes connecting the third and fourth gas sources to the gas supply means,

the method comprising of:

a first step of supplying the first process gas from the first gas source through the first gas introducing pipe to and through the gas supply means onto the substrate within the processing vessel;

a second step of supplying the second process gas from the second gas source through the second gas introducing pipe to and through the gas supply means onto the substrate to reduce the first process gas supplied to the substrate, thereby fanning a film containing refractory metal on the substrate;

a third step of supplying the third process gas from the third gas source through said at least one of the first and second gas introducing pipes to and through the gas supply means onto the film formed on the substrate, thereby nitriding the film of refractory metal formed on the substrate; and

a step of purging the processing vessel by evacuating the processing vessel while supplying the inert gas from the fourth gas source into the processing vessel through said at least one of the first and second gas introducing pipes and the gas supply means,

wherein the first to third steps are repeated with the purging step being carried out between each two of the first to third steps performed so that residual gas present in the processing vessel after performing the first to third steps is reduced to a level of 1 to 30% based on the entire capacity of the processing vessel.

2. The method according to claim 1, wherein the first process gas is WF₆ or W(CO)₆.

3. The method according to claim 1, wherein the first process gas contains WF₆, the second process gas contains SiH₄, and the third process gas contains MMH or NH₃, the second step forming a W film as the film of refractory metal and the third step forming a WN_x film by nitriding the W film.

4. The method according to claim 1, wherein the first process gas contains WF₆, the second process gas contains SiH₄, and the third process gas contains MMH or NH₃, the second step forming a WSi_x film as the film of refractory metal and the third step forming a WSi_x N_y film by nitriding the WSi_x film.

5. The method according to claim 1, wherein the second process gas is selected from a silane gas, a disilane gas or a dichlorosilane gas.

6. The method according to claim 1, wherein the refractory metallic atoms are selected from atoms of Ti, Ta, Mo, Ni, Cr, Co, Nb, Zr, Hf, Pr, Ru, or W.

7. The method according to claim 1, wherein the third step is carried out by evacuating the processing vessel to a vacuum degree of 0.1 Torr.

8. The method according to claim 1, wherein plasma which includes the third process gas is formed to activate N atoms included in the third process gas.

9. The method according to claim 1, further including preventing the first process gas supplied onto the substrate through the gas supply means in the first step and the second process gas supplied onto the substrate through the gas supply means in the second step from being mixed with each other within the gas supply means.

10. The method according to claim 1, wherein the gas supply means includes a showerhead connected to the first gas introducing pipe and the second gas introducing pipe.

11. The method according to claim 10, wherein the gas spray ports are formed in the showerhead and include a first group of gas spray ports and a second group of gas spray ports, the showerhead including a first space communicated with the first gas introducing pip and the first group of gas spray ports and a second space communicated with the second gas introducing pipe and the second group of gas spray ports, so that the gas supplied by the first gas introducing pipe into the processing vessel through the showerhead and the gas supplied by the second gas introducing pipe into the processing vessel through the showerhead are not mixed in the showerhead.

12. A method of forming a film with ALD using a chemical vapor deposition apparatus comprising (i) a processing vessel, (ii) a mounting member which is provided in the processing vessel and supports a substrate thereon, (iii) heating means which heat the substrate supported by the mounting member, (iv) gas supply means having a plurality of gas spray ports for spraying gas onto the substrate in the process vessel, (v) evacuating means for evacuating the gas in the processing vessel so that the gas sprayed onto the substrate flows downwardly, (vi) a first gas source for storing a first process gas, (vii) a second gas source for storing a second process gas, (viii) a third gas source for storing an inert gas, (ix) a first gas introducing pipe which connects the first gas source to the gas supply means, and (x) a second gas introducing pipe which connects the second gas source to the gas supply means, at least one of the first and second gas introducing pipes connecting the third gas source to the gas supply means,

the method comprising of:

a first step of supplying the first process gas from the first gas source through the first gas introducing pipe to and through the gas supply means onto the substrate within the processing vessel;

a second step of supplying the second process gas from the second gas source through the second gas introducing pipe to and through the gas supply means onto the substrate to reduce the first process gas supplied to the substrate, thereby forming a film on the substrate;

a third step of purging the processing vessel by evacuating the processing vessel while supplying the inert gas from the third gas source into the processing vessel through said at least one of the first and second gas introducing pipes and the gas supply means,

wherein the first and second steps are repeated at least once with the third step of purging being carried out between each of the first and second steps and between the second step and the first step of the repetition of the first and second steps such that the third step reduces residual gas remaining after performing the first and second steps to a level of 1 to 30% based on the entire capacity of the processing vessel.

13. The method according to claim 12, wherein the third step is carried out by evacuating the processing vessel to a vacuum degree of 0.1 Torr.

14. The method according to claim 12, wherein the film formed with ALD is made from at least one of SiOF, SiO₂, CF_x(X=1-4), Ta₂O₅, Al₂O₅, HfO₂, ZrO₂, PZT, SBT, ZrSi_xO_y, HfSi_xO_y, IrO, RuO, Pr₂O₃, and La₂O₃.

15. The method according to claim 12, further including preventing the first process gas supplied onto the substrate through the gas supply means in the first step and the second process gas supplied onto the substrate through the gas supply means in the second step from being mixed with each other within the gas supply means.

16. The method according to claim 12, wherein the gas supply means includes a showerhead connected to the first gas introducing pipe and the second gas introducing pipe.

17. The method according to claim 16, wherein the gas spray ports are formed in the showerhead and include a first group of gas spray ports and a second group of gas spray ports, the showerhead including a first space communicated with the first gas introducing pipe and the first group of the gas spray ports and a second space communicated with the second gas introducing pipe and the second group of the gas spray ports, so that the gas supplied by the first gas introducing pipe into the processing vessel through the showerhead and the gas supplied by the second gas introducing pipe into the processing vessel through the showerhead are not mixed in the showerhead.

18. The method according to claim 12, wherein the first process gas contains WF₆ and SiH₄, and the second process gas contains MMH or NH₃, the first step forming a W film on the substrate, and the second step forming a WN_x film by nitriding the W film as the film.

19. The method according to claim 12, wherein the first process gas contains WF₆ and SiH₄, and the second process gas contains MMH or NH₃, the first step forming a WSi_x film on the substrate, and the second step forming a WSi_xN_y film by nitriding the WSi_X film as the film.

20. A method of forming a film with ALD using a chemical vapor deposition apparatus comprising (i) a processing vessel, (ii) a mounting member which is provided in the processing vessel and supports a substrate thereon, (iii) heating means which heat the substrate supported by the mounting member, (iv) gas supply means having a plurality of gas spray ports for spraying gas onto the substrate in the process vessel, (v) evacuating means for evacuating the gas in the processing vessel so that the gas sprayed onto the substrate flows downwardly, (vi) a first gas source for storing a first process gas, (vii) a second gas source for storing a second process gas, (viii) a third gas source for storing an inert gas, (ix) a first gas introducing pipe which connects the first gas source to the gas supply means, and (x) a second gas introducing pipe which connects the second gas source to the gas supply means, at least one of the first and second gas introducing pipes connecting the third gas source to the gas supply means,

the method comprising of:

a first step of supplying the first process gas from the first gas source through the first gas introducing pipe to and through the gas supply means onto the substrate within the processing vessel;

a second step of supplying the second process gas from the second gas source through the second gas introducing pipe to and through the gas supply means onto the substrate to reduce the first process gas supplied to the substrate, thereby forming a film on the substrate;

a third step of purging the processing vessel by evacuating the processing vessel while supplying the inert gas from the third gas source into the processing vessel through said at least one of the first and second gas introducing pipes and the gas supply means,

wherein the first and second steps are repeated with the third step of purging being carried out between each of the first and second steps and between the second step and the first step of each repetition of the first and second steps so that the third step reduces residual gas in the processing vessel, including residual gas absorbed on an inner wall of the processing vessel, due to the previous performance of the first or second steps to a level of 1 to 30% based on the entire capacity of the processing vessel.

21. The method according to claim 20, wherein the third step is carried out by evacuating the processing vessel to a vacuum degree of 0.1 Torr.

22. The method according to claim 20, wherein the film formed with ALD is made from at least one of SiOF, SiO₂, CF_x(X=1-4), Ta₂O₅, Al₂O₅, HfO₂, ZrO₂, PZT, SBT, ZrSi_xO_y, HfSi_xO_y, IrO, RuO, Pr₂O₃, and La₂O₃.

23. The method according to claim 20, further including preventing the first process gas supplied onto the substrate through the gas supply means in the first step and the second process gas supplied onto the substrate through the gas supply means in the second step from being mixed with each other within the gas supply means.

24. The method according to claim 20, wherein the gas supply means includes a showerhead connected to the first gas introducing pipe and the second gas introducing pipe.

25. The method according to claim 24, wherein the gas spray ports are formed in the showerhead and include a first group of gas spray ports and a second group of gas spray ports, the showerhead including a first space communicated with the first gas introducing pip and the first group of the gas spray ports and a second space communicated with the second gas introducing pipe and the second group of the gas spray ports, so that the gas supplied by the first gas introducing pipe into the processing vessel through the showerhead and the gas supplied by the second gas introducing pipe into the processing vessel through the showerhead are not mixed in the showerhead.

28. The method according to claim 20, further including preventing the first process gas supplied onto the substrate through the gas supply means in the first step and the second process gas supplied onto the substrate through the gas supply means in the second step from being mixed with each other within the gas supply means.

26. A method of forming a film with ALD using a chemical vapor deposition apparatus comprising (i) a processing vessel, (ii) a mounting member which is provided in the processing vessel and supports a substrate thereon, (iii) heating means which heat the substrate supported by the mounting member, (iv) gas supply means having a plurality of gas spray ports for spraying gas onto the substrate in the process vessel, (v) evacuating means for evacuating the gas in the processing vessel so that the gas sprayed onto the substrate flows downwardly, (vi) a first gas source for storing a first process gas, (vii) a second gas source for storing a second process gas, (viii) a third gas source for storing an inert gas, (ix) a first gas introducing pipe which connects the first gas source to the gas supply means, and (x) a second gas introducing pipe which connects the second gas source to the gas supply means, at least one of the first and second gas introducing gas pipes connecting the third gas source to the gas supply means,

the method comprising of:

a first step of supplying the first process gas from the first gas source through the first gas introducing pipe to and through the gas supply means onto the substrate within the processing vessel;

a second step of supplying the second process gas from the second gas source through the second gas introducing pipe to and through the gas supply means onto the substrate to reduce the first process gas supplied to the substrate, thereby forming a film containing refractory metal on the substrate;

a third step of purging the processing vessel by evacuating the processing vessel while supplying the inert gas from the third gas source into the processing vessel through said at least one of the first and second gas introducing pipes and the gas supply means,

wherein the first and second steps are repeated with the third step of purging being carried out between each of the first and second steps and between the second step and the first step of each repetition of the first and second steps, with the third step being carried out by evacuating the processing vessel to a vacuum degree of 0.1 Torr so as to reduce a total quantity of residual gas in the processing vessel, including residual gas absorbed on an inner wall of the processing vessel, due to the previous performance of the first or second steps to a level of 1 to 30% based on the entire capacity of the processing vessel.

27. The method according to claim 26, wherein the film formed with ALD is made from at least one of SiOF, SiO₂, CF_x(X=1-4), Ta₂O₅, Al₂O₅, HfO₂, ZrO₂, PZT, SBT, ZrSi_xO_y, HfSi_xO_y, IrO, RuO, Pr₂O₃, and La₂O₃.

29. The method according to claim 26, wherein the gas supply means includes a showerhead connected to the first gas introducing pipe and the second gas introducing pipe.

30. The method according to claim 29, wherein the gas spray ports are formed in the showerhead and include a first group of gas spray ports and a second group of gas spray ports, the showerhead including a first space communicated with the first gas introducing pip and the first group of the gas spray ports and a second space communicated with the second introducing pipe and the second group of the gas spray ports, so that the gas supplied by the first gas introducing pipe into the processing vessel through the showerhead and the gas supplied by the second gas introducing pipe into the processing vessel through the showerhead are not mixed in the showerhead.

31. A method of forming a film with ALD using a chemical vapor deposition apparatus comprising (i) a processing vessel, (ii) a mounting member which is provided in the processing vessel and supports a substrate thereon, (iii) heating means which heat the substrate supported by the mounting member, (iv) gas supply means having a plurality of gas spray ports for spraying gas onto the substrate in the process vessel, (v) evacuating means for evacuating the gas in the processing vessel so that the gas sprayed onto the substrate flows downwardly, (vi) a first gas source for storing a first process gas including refractory metallic atoms, (vii) a second gas source for storing a second process gas including a reducing gas, (viii) a third gas source for storing an inert gas, (ix) a first gas introducing pipe which connects the first gas source to the gas supply means, and (x) a second gas introducing pipe which connects the second gas source to the gas supply means, at least one of the first and second gas introducing pipes connecting the third gas source to the gas supply means,

the method comprising of:

a first step of supplying the first process gas from the first gas source onto the substrate within the processing vessel, through the first gas introducing pipe and the gas supply means;

a second step of supplying the second process gas from the second gas source onto the substrate to reduce the first process gas supplied to the substrate, through the second gas introducing pipe and the gas supply means, thereby forming a film of refractory metal on the substrate; and

a step of purging the processing vessel by evacuating the processing vessel while supplying the inert gas into the processing vessel from the third gas source, through said at least one of the first and second introducing pipes and the gas supply means,

the first and second steps being repeately several times, and the purging step being carried out between the first and second steps, and the purging step reducing the residual gas which has been supplied in the processing vessel by the previous step of first and second steps to a level of 1 to 30% based on the entire capacity of the processing vessel.

32. The method according to claim 31, wherein the third step is carried out by evacuating the processing vessel to a vacuum degree of 0.1 Torr.