Titanium aluminum and tantalum aluminum thin films

Patent metadata

Field	Value
Publication number	US-10002936-B2
Application number	US-201514919180-A
Country	US
Kind code	B2
Filing date	Oct 21, 2015
Priority date	Oct 23, 2014
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

A process for depositing titanium aluminum or tantalum aluminum thin films comprising nitrogen on a substrate in a reaction space can include at least one deposition cycle. The deposition cycle can include alternately and sequentially contacting the substrate with a vapor phase Ti or Ta precursor and a vapor phase Al precursor. At least one of the vapor phase Ti or Ta precursor and the vapor phase Al precursor may contact the substrate in the presence of a vapor phase nitrogen precursor.

First claim

What is claimed is:

1. A process for depositing a titanium aluminum thin film comprising nitrogen and having a work function of less than 4.5 eV on a substrate in a reaction space, the process comprising at least one deposition cycle comprising alternately and sequentially contacting the substrate with a vapor phase Ti precursor and a vapor phase Al precursor at a temperature of 300° C. to 400° C., wherein the vapor phase Ti precursor comprises TiCl 4 and the vapor phase Al precursor comprises tritertbutylaluminum (TTBA), and wherein at least one of the vapor phase Ti precursor and the vapor phase Al precursor contacts the substrate in the presence of a vapor phase nitrogen precursor.

2. The process of claim 1 , wherein vapor phase nitrogen precursor is introduced into the reaction space concurrently with one or both of the Ti precursor and the Al precursor.

3. The process of claim 2 , wherein the vapor phase nitrogen precursor serves as a carrier gas for one or both of the Ti precursor and the Al precursor.

4. The process of claim 1 , wherein the vapor phase nitrogen precursor comprises N 2 .

5. The process of claim 1 , wherein excess precursor and reaction byproducts, if any, are removed from the reaction space after contacting the substrate with the vapor phase Ti precursor and before subsequently contacting the substrate with the vapor phase Al precursor.

6. The process of claim 5 , wherein the vapor phase nitrogen precursor flows into the reaction space throughout the deposition cycle and aids in the removal of excess precursor and reaction byproducts, if any, from the reaction space.

7. The process of claim 1 , wherein the titanium aluminum thin film comprises up to about 40% carbon on an atomic basis.

8. The process of claim 1 , wherein the titanium aluminum thin film comprises up to about 25% nitrogen on an atomic basis.

9. The process of claim 1 , wherein the process is an atomic layer deposition process.

10. The process of claim 1 , wherein at least one of the reactants at least partially decomposes on the substrate surface.

11. A process for depositing a titanium aluminum thin film comprising nitrogen and having a work function of less than 4.5 eV on a substrate in a reaction space, the process comprising one or more deposition cycles comprising:
contacting the substrate with a first vapor phase precursor comprising TiC 1 4 ;
removing excess first vapor phase precursor and reaction byproducts, if any, from the substrate;
contacting the substrate with a second vapor phase precursor comprising TTBA; and
removing excess second vapor phase precursor and reaction byproducts, if any, from the substrate;
wherein at least one of the contacting the substrate with a first vapor phase precursor comprising TiCl 4 and contacting the substrate with a second vapor phase precursor comprising TTBA steps occurs in the presence of a nitrogen precursor comprising N 2 , and
wherein the one or more deposition cycles are carried out at a temperature of 300° C. to 400° C.

12. The method of claim 11 , wherein the titanium aluminum thin film comprising nitrogen comprises up to about 25% nitrogen on an atomic basis.

13. The method of claim 11 , wherein the titanium aluminum thin film comprising nitrogen comprises up to about 40% carbon on an atomic basis.

14. The method of claim 11 , wherein the nitrogen precursor comprising N 2 is introduced into the reaction space as a carrier gas for each of the first vapor phase precursor comprising TiCl 4 and the second vapor phase precursor comprising TTBA.

15. The method of claim 14 , wherein removing excess second vapor phase precursor comprising TTBA comprises continuing to flow the nitrogen precursor comprising N 2 into the reaction space without providing second vapor phase precursor comprising TTBA.

16. The method of claim 14 , wherein removing excess first vapor phase precursor comprising TiCl 4 comprises continuing to flow the nitrogen precursor comprising N 2 without providing first vapor phase precursor comprising TiCl 4 .

17. The method of claim 11 , wherein a deposition cycle is repeated two or more times to deposit a TiAl film comprising nitrogen to a desired thickness.

18. The method of claim 17 , wherein both first vapor phase precursor comprising TiCl 4 and the second vapor phase precursor comprising TTBA contact the substrate in the presence of a nitrogen precursor comprising N 2 in each deposition cycle.

19. A process for depositing a titanium aluminum thin film comprising nitrogen and having a work function of less than 4.5 eV on a substrate in a reaction space, the process comprising at least one deposition cycle comprising:
contacting the substrate with a first vapor phase precursor comprising TiCl 4 ;
removing excess first vapor phase precursor and reaction byproducts, if any, from the substrate;
contacting the substrate with a second vapor phase precursor comprising TTBA; and
removing excess second vapor phase precursor and reaction byproducts, if any, from the substrate;
wherein the substrate is contacted with the first and second vapor phase precursors at a temperature of 300° C. to 400° C. and at least one of the contacting the substrate with a first vapor phase precursor comprising TiCl 4 and contacting the substrate with a second vapor phase precursor comprising TTBA steps occurs in the presence of a nitrogen precursor comprising N 2 ;
contacting the substrate with a protective treatment reagent comprising a silane or borane; and
repeating at least the first vapor phase precursor and second vapor phase precursor contacting and removing steps until TiAl thin film comprising nitrogen of the desired thickness has been formed.

20. The process of claim 19 , wherein the substrate is contacted with a protective treatment reagent comprising a silane or borane in each deposition cycle.

21. The process of claim 19 , wherein the silane or borane is selected from the group consisting of monosilane, disilane, trisilane, borane, diborane, and triborane.

22. The process of claim 19 , wherein the substrate is only contacted with a protective treatment reagent comprising a silane or borane after every 2, 5, 10, 20 or more deposition cycles.

Assignees

• Asm Ip Holding Bv

Inventors

• Haukka Suvi
• Givens Michael
• Shero Eric
• Winkler Jerry
• Räisänen Petri
• Asikainen Timo
• Zhu chiyu
• Anttila Jaakko

Classifications

• H10P14/432

  using selective deposition · CPC title

• H10P14/412 Primary

  Deposition of metallic or metal-silicide materials · CPC title

• H10P14/43

  Chemical deposition, e.g. chemical vapour deposition [CVD] · CPC title

• 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

• C23C16/34

  Nitrides {(C23C16/303 takes precedence)} · CPC title