Deposition of smooth metal nitride films

Patent metadata

Field	Value
Publication number	US-9412602-B2
Application number	US-201313802157-A
Country	US
Kind code	B2
Filing date	Mar 13, 2013
Priority date	Mar 13, 2013
Publication date	Aug 9, 2016
Grant date	Aug 9, 2016

Abstract

In one aspect, methods of forming smooth ternary metal nitride films, such as Ti x W y N z films, are provided. In some embodiments, the films are formed by an ALD process comprising multiple super-cycles, each super-cycle comprising two deposition sub-cycles. In one sub-cycle a metal nitride, such as TiN is deposited, for example from TiCl 4 and NH 3 , and in the other sub-cycle an elemental metal, such as W, is deposited, for example from WF 6 and Si 2 H 6 . The ratio of the numbers of each sub-cycle carried out within each super-cycle can be selected to achieve a film of the desired composition and having desired properties.

First claim

We claim:

1. An atomic layer deposition (ALD) process for depositing a metal nitride film on a substrate, the process comprising a plurality of super-cycles, each super-cycle comprising a TiN sub-cycle and a W sub-cycle,
wherein the TiN sub-cycle comprises alternately and sequentially contacting the substrate with a titanium precursor and a nitrogen reactant;
wherein the W sub-cycle comprises alternately and sequentially contacting the substrate with a tungsten precursor and a second precursor, wherein the second precursor is a silane or borane; and
wherein the film comprises a mixed metal nitride.

2. The process of claim 1 , wherein the titanium precursor is a titanium halide or metal-organic titanium compound and the tungsten precursor is a tungsten halide or metal-organic tungsten compound.

3. The process of claim 2 , wherein the titanium precursor is TiCl 4 and the tungsten precursor is WF 6 .

4. The process of claim 1 , wherein the nitrogen reactant is selected from the group consisting of ammonia, N 2 H 4 , nitrogen atoms, nitrogen containing plasma and nitrogen radicals.

5. The process of claim 1 , wherein the second precursor comprises disilane or trisilane.

6. The process of claim 1 , wherein the TiN sub-cycle and the W sub-cycle are carried out at a ratio of at least about 3 in at least one of the plurality of super-cycles.

7. The method of claim 1 , wherein the film forms a continuous layer.

8. A method for forming a film comprising a mixed metal nitride on a substrate in a reaction chamber, the method comprising:
conducting an atomic layer deposition super-cycle comprising a metal nitride sub-cycle and an elemental metal sub-cycle,
wherein the first metal nitride sub-cycle comprises:
pulsing a first vapor-phase metal precursor comprising a first metal (M 1 ) into the reaction chamber to form at most a molecular monolayer of the metal precursor on the substrate; and
pulsing a vapor phase nitrogen reactant into the reaction chamber, where the nitrogen reactant reacts with the metal precursor on the substrate to form a metal nitride; and

wherein the second elemental metal sub-cycle comprises:
pulsing a second vapor phase metal precursor comprising a second different metal (M 2 ) into the reaction chamber to form at most a molecular monolayer of second metal precursor on the substrate; and
pulsing a vapor phase second reactant into the reaction chamber that reacts with the second metal precursor to form elemental metal; and

repeating the atomic layer deposition super-cycle to form a ternary metal nitride film of the desired thickness, the ternary metal nitride film having the formula M 1 x M 2 y N z , wherein x is from 0 to 1.5, y is from 0.05 to 4 and z is from 0 to 2, and
wherein each super-cycle comprises up to ten repetitions of the second elemental metal sub-cycle, and wherein a ratio of the first metal nitride sub-cycle to the second elemental metal sub-cycle in each super-cycle is 0.5 to 40.

9. The method of claim 8 , wherein M 1 is selected from Ti, Ta, Nb, Mo and W and M 2 is selected from Mo and W.

10. The method of claim 8 , wherein the first metal precursor comprises a metal halide or metal-organic compound.

11. The method of claim 8 , wherein the second metal precursor comprises a metal halide or metal-organic compound.

12. The method of claim 8 , wherein the second reactant comprises a silane or borane.

13. The method of claim 8 , wherein the nitrogen reactant comprises ammonia, N 2 H 4 , nitrogen atoms, nitrogen containing plasma or nitrogen radicals.

14. The method of claim 8 , wherein the metal nitride film does not have a columnar grain structure.

15. A method for forming a film comprising a mixed metal nitride on a substrate in a reaction chamber, the method comprising:
a first metal nitride sub-cycle comprising:
contacting the substrate with a first vapor-phase metal precursor comprising a first metal to form at most a molecular monolayer of the metal precursor on the substrate; and
contacting the substrate with a vapor phase nitrogen reactant, such that the nitrogen reactant reacts with the metal precursor on the substrate to form a metal nitride; and

a second elemental metal sub-cycle comprising:
contacting the substrate with a second vapor phase metal precursor comprising a second metal different from the first metal to form at most a molecular monolayer of second metal precursor on the substrate; and
contacting the substrate with a vapor phase second reactant that reacts with the second metal precursor to form elemental metal; and

repeating the first and second sub-cycles to form a ternary metal nitride film of a desired thickness,
wherein the ternary metal nitride film has a roughness of less than 2 nm as measured by x-ray reflectivity.

16. The method of claim 15 , wherein the second elemental metal sub-cycle is performed before the first metal nitride sub-cycle.

17. The method of claim 15 , wherein the first metal is selected from Ti, Ta, Nb, Mo and W and the second metal is selected from Mo and W.

18. The method of claim 15 , wherein the second reactant comprises a silane or borane.

19. The method of claim 15 , wherein the first sub-cycle and second sub-cycle are repeated at a selected ratio in a plurality of super-cycles.

20. The method of claim 19 , wherein the first sub-cycle is repeated no more than about 40 times consecutively and the second sub-cycle is repeated no more than about 10 times consecutively in each of the plurality of super-cycles.

21. The method of claim 15 , wherein the roughness of less than about 2 nm is at a film thickness of about 20 to about 50 nm.

Assignees

• Asm Ip Holding Bv

Inventors

• Blomberg Tom E
• Anttila Jaakko

Classifications

• H10D64/01318

  the conductor comprising a layer of alloy material, compound material or organic material contacting the insulator, e.g. TiN (comprising a layer of alloys of Si, Ge or C H10D64/01314) · CPC title

• H10P14/432

  using selective deposition · CPC title

• H10W20/425

  Barrier, adhesion or liner layers · CPC title

• H10W20/033

  in openings in dielectrics · CPC title

• H10W20/062 Primary

  by smoothing of conductive parts, e.g. by planarisation · CPC title