Method of film deposition using activated precursor gases

• US 20040018304A1
• Filed: 07/10/2002
• Published: 01/29/2004
• Est. Priority Date: 07/10/2002
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Chung, Hua, Chen, Ling, Ku, Vincent W.
• Granted Patent: US 6,838,125 B2
• Time in Patent Office: Days
• US Class Current: 427/250
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/4488 by in situ generation of reactive gas by chemical or electrochemical reaction
• CPC Class Codes: C23C 16/452 by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]

Abstract

A method for depositing a film on a substrate is provided. In one aspect, the method includes providing a metal-containing precursor to an activation zone, and activating the metal-containing precursor to form an activated precursor. The activated precursor gas is transported to a reaction chamber, and a film is deposited on the substrate using a cyclical deposition process, wherein the activated precursor gas and a reducing gas are alternately adsorbed on the substrate. Also provided is a method of depositing a film on a substrate using an activated reducing gas.

Claims

1. A method for depositing a film on a substrate surface, comprising:

providing a metal-containing precursor to an activation zone;

activating the metal-containing precursor to form an activated metal precursor; and

alternately adsorbing the activated precursor and a first reducing gas to deposit a film on the substrate surface.

2. The method of claim 1, wherein activating the metal-containing precursor comprises contacting the metal-containing precursor with a condensed phase material containing a metal selected from the group consisting of zinc, magnesium, and combinations thereof.

3. The method of claim 1, wherein activating the metal-containing precursor comprises reacting the metal-containing precursor with a gas phase material containing one or more metallic species selected from the group consisting of sodium, potassium, rubidium, cesium, francium, lithium, beryllium, magnesium, calcium, strontium, barium, radium, and combinations thereof.

4. The method of claim 3, wherein the gas phase material comprises ammonia.

5. The method of claim 1, wherein activating the metal-containing precursor comprises reacting the metal-containing precursor with a plasma of hydrogen radicals, nitrogen radicals, or hydrogen and nitrogen radicals.

6. The method of claim 1, wherein activating the metal-containing precursor comprises exciting a gas phase material with a radiation source and reacting the gas phase material with the metal-containing precursor.

7. The method of claim 1 wherein the film comprises a material selected from the group consisting of tantalum, tantalum nitride, titanium, titanium nitride, tungsten, tungsten nitride, and combinations thereof.

8. The method of claim 1 wherein the metal-containing precursor comprises a material selected from the group consisting of Ta(NMe₂)₅ (PDMAT), Ta(NEt₂)₅ (PDEAT), Ta(NMeEt)₅ (PEMAT), (Net₂)₃TaN-Bu (TBTDET), (Net₂Me)₃TaN-Bu (TBTMET), (NMe₂)₃TaN-Bu (TBTDMT), tantalum chloride (TaCl₅), tantalum bromide (TaBr₅), tantalum iodide (Tal₅), tantalum hydrides (Cp)₂TaH₃, (CpMe)₂TaH₃, TDMAT, PDEAT, titanium chloride (TiCl₄), and combinations thereof.

9. The method of claims 1 wherein the first reducing gas is selected from the group consisting of ammonia (NH₃), hydrogen, nitrogen, hydrazine (N₂H₄), monomethyl hydrazine (CH₃N₂H₃), dimethyl hydrazine (C₂H₆N₂H₂), t-butyl hydrazine (C₄H₉N₂H₃), phenyl hydrazine (C₆H₅N₂H₃), 2,2′

-azoisobutane ((CH₃)₆C₂N₂), ethylazide (C₂H₅N₃), silane (SiH₄), disilane (Si₂H₆), dichlorosilane (SiCl₂H₂), borane (BH₃), diborane (B₂H₆), triborane (B₃H₉), tetraborane (B₄H₁₂), pentaborane (B₅H₁₅), hexaborane (B₆H₁₈), heptaborane (B₇H₂₁), octaborane (B₈H₂₄), nanoborane (B₉H₂₇) and decaborane (B₁₀H₃₀), and combinations thereof.

10. The method of claim 1 wherein the cyclical deposition process comprises a plurality of cycles, wherein each cycle comprises establishing a flow of an inert gas to the process chamber and modulating the flow of the inert gas with an alternating period of exposure to one of either the activated precursor gas or the first reducing gas.

11. A method for depositing a film on a substrate, comprising:

providing a first reducing gas to an activation zone;

activating the first reducing gas to form an activated reducing gas; and

depositing a film on the substrate using a cyclical deposition process, wherein the activated reducing gas and a metal-containing precursor are alternately adsorbed on the substrate.

12. The method of claim 11 wherein activating the first reducing gas comprises igniting the first reducing gas into a plasma state, exciting the first reducing gas with a radiation source, or a combination thereof.

13. The method of claim 11 wherein the film comprises a material selected from the group consisting of tantalum, tantalum nitride, titanium, titanium nitride, and combinations thereof.

14. The method of claim 11 wherein the cyclical deposition process comprises a plurality of cycles, wherein each cycle comprises adsorbing one or more second reducing gases between adsorbing the activated reducing gas and adsorbing the precursor gas.

15. A method for forming a interconnect, comprising:

providing a metal-containing precursor to an activation zone;

activating the metal-containing precursor to form an activated precursor gas;

providing a first reducing gas to an activation zone;

activating the first reducing gas to form an activated reducing gas; and

depositing a film on the substrate using a cyclical deposition process, wherein the activated reducing gas and a metal-containing precursor are alternately adsorbed on the substrate.

16. The method of claim 15 wherein activating the metal-containing precursor comprises contacting the metal-containing precursor with a condensed phase material containing a metal selected from the group consisting of zinc, magnesium, and combinations thereof.

17. The method of claim 16 wherein activating the metal-containing precursor comprises reacting the metal-containing precursor with a gas phase material containing one or more metallic species selected from the group consisting of sodium, potassium, rubidium, cesium, francium, lithium, beryllium, magnesium, calcium, strontium, barium, radium, and combinations thereof.

18. The method of claim 17 wherein the gas phase material comprises ammonia.

19. The method of claim 15 wherein activating the metal-containing precursor comprises igniting a gas phase material into a plasma state and reacting the gas phase material with the metal precursor gas.

20. The method of claim 15 wherein activating the metal-containing precursor comprises exciting a gas phase material with a radiation source and reacting the gas phase material with the metal precursor gas.

21. The method of claim 15 wherein the film comprises a material selected from the group consisting of tantalum, tantalum nitride, titanium, titanium nitride, and combinations thereof.

22. The method of claim 15 wherein the metal-containing precursor comprises a material selected from the group consisting of Ta(NMe₂)₅ (PDMAT), Ta(NEt₂)₅ (PDEAT), Ta(NMeEt)₅ (PEMAT), (Net₂)₃TaN-Bu (TBTDET), (Net₂Me)₃TaN-Bu (TBTMET), (NMe₂)₃TaN-Bu (TBTDMT), tantalum chloride (TaCl₅), tantalum bromide (TaBr₅), tantalum iodide (Tal₅), tantalum hydrides (Cp)₂TaH₃, (CpMe)₂TaH₃, TDMAT, PDEAT, titanium chloride (TiCl₄), and combinations thereof.

23. The method of claim 15 wherein the first reducing gas is selected from the group consisting of ammonia (NH₃), hydrogen, nitrogen, hydrazine (N₂H₄), monomethyl hydrazine (CH₃N₂H₃), dimethyl hydrazine (C₂H₆N₂H₂), t-butyl hydrazine (C₄H₉N₂H₃), phenyl hydrazine (C₆H₅N₂H₃), 2,2′

-azoisobutane ((CH₃)₆C₂N₂), ethylazide (C₂H₅N₃), silane (SiH₄), disilane (Si₂H₆), dichlorosilane (SiCl₂H₂), borane (BH₃), diborane (B₂H₆), triborane (B₃H₉), tetraborane (B₄H₁₂), pentaborane (B₅H₁₅), hexaborane (B₆H₁₈), heptaborane (B₇H₂₁), octaborane (B₈H₂₄), nanoborane (B₉H₂₇) and decaborane (B₁₀H₃₀), and combinations thereof.

24. A method of forming a interconnect, comprising:

providing a substrate structure having an aperture formed thereon to a reaction chamber;

providing ammonia gas to an activation zone;

activating the ammonia gas; and

depositing a barrier layer on the substrate structure using a cyclical deposition process, wherein the activated ammonia gas and PDMAT are alternately adsorbed on the substrate structure.

25. The method of claim 24 wherein activating the ammonia gas comprises igniting the ammonia gas into a plasma state using RF power of about 1,000 W at 13.56 mHz.

26. The method of claim 24 wherein activating the ammonia gas comprises heating the ammonia gas to a temperature between about 500°

C. and about 1,000°

C.

27. The method of claim 24 wherein the film comprises a material selected from the group consisting of tantalum, tantalum nitride, titanium, titanium nitride, and combinations thereof.