Ti, Ta, Hf, Zr and related metal silicon amides for ALD/CVD of metal-silicon nitrides, oxides or oxynitrides

• US 20070082500A1
• Filed: 09/18/2006
• Published: 04/12/2007
• Est. Priority Date: 10/07/2005
• Status: Active Grant

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Lei, Xinjian, Norman, John
• Granted Patent: US 7,754,906 B2
• Time in Patent Office: Days
• US Class Current: 438/758
• CPC Class Codes: C07F 11/005 compounds without a metal-carbon linkage
• CPC Class Codes: C07F 7/003 without C-Metal linkages
• CPC Class Codes: C07F 9/005 Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages

Abstract

An organometallic complex represented by the structure:
wherein M is a metal selected from Group 4 of the Periodic Table of the Elements and R^1-4 can be same or different selected from the group consisting of dialkylamide, difluoralkylamide, hydrogen, alkyl, alkoxy, fluoroalkyl and alkoxy, cycloaliphatic, and aryl with the additional provision that when R¹ and R² are dialkylamide, difluoralkylamide, alkoxy, fluoroalkyl and alkoxy, they can be connected to form a ring. Related compounds are also disclosed. CVD and ALD deposition processes using the complexes are also included.

Claims

1. An organometallic complex represented by the structure:

wherein M is a metal selected from Group 4 of the Periodic Table of the Elements and R^1-4 can be same or different selected from the group consisting of dialkylamide, difluoralkylamide, hydrogen, alkyl, alkoxy, fluoroalkoxy, fluoroalkyl and alkoxy, cycloaliphatic, and aryl with the additional provision that when R¹ and R² are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy, or fluoroalkyl, they can be connected to form a ring.

2. The organometallic complex of claim 1 wherein M is selected from the group consisting of titanium, zirconium and hafnium.

3. The organometallic complex of claim 1 comprising, bis(N,N′

-di(tert-butyl)-diaminosilyl)titanium.

4. In a deposition process for forming conformal metal silicon nitride thin film on a substrate wherein an organometallic complex of claim 1 is introduced to a deposition chamber, vaporized and deposited on a substrate.

5. The deposition process of claim 4 is selected from the group consisting of an atomic layer deposition(ALD) process and a chemical vapor deposition (CVD) process, optionally with ammonia.

6. An ALD or CVD process using a precursor of claim 1 reacted with a nitrogen containing reagent selected from the group consisting of ammonia, hydrazine, dimethylhydrazine and nitrogen, in a reaction condition selected from the group consisting of thermal, plasma, remote plasma and other energizing environment to form a metal silicon nitride-based film.

7. An ALD or CVD process using a precursor from claim 1 reacted with a reagent selected from the group consisting of an oxidizing reagent and mixture of oxidizing and nitrogen containing reagents, in a reaction condition selected from the group consisting of thermal, plasma, remote plasma and other energizing environment, to form a metal silicon oxide or oxynitride-based film.

8. The process of claim 4 using an additional treatment step for final film densification or film annealing, is selected from the group consisting of thermal, ozone, plasma, UV and microwave.

9. An organometallic complex represented by the structure:

wherein M is a metal selected from Group 4 of the Periodic Table of the Elements and R^5-10 can be same or different selected from the group consisting of hydrogen, alkyl, alkoxy, fluoroalkyl alkoxy, fluoroalkoxy, cycloaliphatic, and aryl with the additional provision that when R⁵, R⁶, R⁹ and R¹⁰ are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy or fluoroalkyl, they can be connected to form a ring.

10. The organometallic complex of claim 9 wherein M is selected from the group consisting of titanium, zirconium and hafnium.

11. A deposition process for forming a conformal metal silicon nitride thin film on a substrate, wherein an organometallic complex of claim 9 is introduced to a deposition chamber, vaporized and deposited on a substrate.

12. The deposition process of claim 11 is selected from the group consisting of an atomic layer deposition(ALD) process and a chemical vapor deposition (CVD) process, optionally with ammonia.

13. An ALD or CDV process wherein a precursor of claim 9 is reacted with a nitrogen containing reagent selected from the group consisting of ammonia, hydrazine, dimethylhydrazine and nitrogen, in a reaction condition selected from the group consisting of thermal, plasma, remote plasma and other energizing environment, to form a metal silicon nitride-based film.

14. An ALD or CVD process wherein a precursor of claim 9 is reacted with a reagent selected from the group consisting of an oxidizing reagent and a mixture of oxidizing and nitrogen containing reagents, in a reaction condition selected from the group consisting of thermal, plasma, remote plasma and other energizing environment, to form a metal silicon oxide or oxynitride-based film.

15. The process of claim 11 using an additional treatment step for final film densification or film annealing, is selected from the group consisting of thermal, ozone, plasma, UV and microwave.

16. An organometallic complex represented by the structure:

wherein M is a metal selected from Group 5 of the Periodic Table of the Elements and R^11-16 can be same or different selected from the group consisting of, hydrogen, alkyl, alkoxy, fluoroalkoxy, fluoroalkyl and cycloaliphatic, and aryl;

n=1,2, m=5−

2n, wherein when R¹¹, R¹², R¹⁵ and R¹⁶ are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy or fluoroalkyl they can be connected to form a ring.

17. The organometallic complex of claim 16 wherein M is selected from the group consisting of vanadium, niobium, and tantalum.

18. A deposition process for forming a conformal metal silicon nitride thin film on a substrate, wherein an organometallic complex of claim 16 is introduced into a deposition chamber, vaporized and deposited on a substrate.

19. The deposition process of claim 18 is selected from the group consisting of an atomic layer deposition(ALD) process and a chemical vapor deposition (CVD) process, optionally with ammonia.

20. An ALD or CDV process wherein a precursor of claim 16 is reacted with a nitrogen containing reagent selected from the group consisting of ammonia, hydrazine, dimethylhydrazine and nitrogen, in a reaction condition selected from the group consisting of thermal, plasma, remote plasma and other energizing environment, to form a metal silicon nitride-based film.

21. An ALD or CVD process wherein a precursor of claim 16 is reacted with a reagent selected from the group consisting of an oxidizing reagent and a mixture of oxidizing and nitrogen containing reagents in a reaction process selected from the group consisting of thermal, plasma, remote plasma and other energizing environment, to form a metal silicon oxide or oxynitride-based film.

22. The process of claim 18 using an additional treatment step for final film densification or film annealing, is selected from the group consisting of thermal, ozone, plasma, UV and microwave.

23. An organometallic complex represented by the structure:

wherein M is a metal selected from Group 6 of the Periodic Table of the Elements and R^17-22 can be same or different selected from the group consisting of, hydrogen, alkyl, alkoxy, fluoroalkyl and alkoxy, cycloaliphatic, and aryl;

p=1,2,3, q=6−

2p, wherein when R¹⁷, R¹⁸, R²¹ and R²² are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy, or fluoroalkyl and, they can be connected to form a ring.

24. The organometallic complex of claim 23 wherein M is selected from the group consisting of chromium, molybdenum and tungsten.

25. A deposition process for forming a conformal metal silicon nitride thin film on a substrate, wherein an organometallic complex of claim 23 is introduced into a deposition chamber, vaporized and deposited on the substrate.

26. The deposition process of claim 25 is selected from the group consisting of an atomic layer deposition(ALD) process and a chemical vapor deposition (CVD) process, optionally with ammonia.

27. An ALD or CVD process wherein a precursor of claim 23 is reacted with a nitrogen containing reagent selected from the group consisting of ammonia, hydrazine, dimethylhydrazine and nitrogen, in a reaction condition selected from the group consisting of thermal, plasma, remote plasma and other energizing environment, to form a metal silicon nitride-based film.

28. An ALD or CVD process wherein a precursor of claim 23 is reacted with a reagent selected from the group consisting of an oxidizing reagent and a mixture of oxidizing and nitrogen containing reagents, under a reaction condition selected from the group consisting of thermal, plasma, remote plasma and other energizing environment, to form a metal silicon oxide or oxynitride-based film.

29. A cyclic deposition process to form a metal silicon nitride film on a substrate comprising the steps:

introducing an organometallic precursor to a deposition chamber and depositing a film on a heated substrate;

purging the deposition chamber to remove unreacted organometallic precursor and any byproduct;

introducing a metal amide to deposit a film on a heated substrate;

purging the deposition chamber to remove any unreacted metal amide and byproduct; and

,

repeating the cyclic deposition process until a desired thickness of film is established.

30. The process of claim 29 wherein the organometallic complex is selected from the group consisting of

(a)

 

wherein M is a metal selected from Group 4 of the Periodic Table of the Elements and R^1-4 can be same or different selected from the group consisting of dialkylamide, difluoralkylamide, hydrogen, alkyl, alkoxy, fluoroalkoxy, fluoroalkyl and alkoxy, cycloaliphatic, and aryl with the additional provision that when R¹ and R² are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy, or fluoroalkyl, they can be connected to form a ring;

(b)

 

wherein M is a metal selected from Group 4 of the Periodic Table of the Elements and R^5-10 can be same or different selected from the group consisting of hydrogen, alkyl, alkoxy, fluoroalkyl alkoxy, fluoroalkoxy, cycloaliphatic, and aryl with the additional provision that when R⁵, R⁶, R⁹ and R¹⁰ are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy or fluoroalkyl, they can be connected to form a ring;

(c)

 

wherein M is a metal selected from Group 5 of the Periodic Table of the Elements and R^11-16 can be same or different selected from the group consisting of, hydrogen, alkyl, alkoxy, fluoroalkoxy, fluoroalkyl and cycloaliphatic, and aryl;

n=1,2, m=5−

2n, wherein when R¹¹, R¹², R¹⁵ and R¹⁶ are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy or fluoroalkyl they can be connected to form a ring; and

(d)

 

wherein M is a metal selected from Group 6 of the Periodic Table of the Elements and R^17-22 can be same or different selected from the group consisting of, hydrogen, alkyl, alkoxy, fluoroalkyl and alkoxy, cycloaliphatic, and aryl;

p=1,2,3, q=6−

2p, wherein when R¹⁷, R¹⁸, R²¹ and R²² are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy, or fluoroalkyl and, they can be connected to form a ring.

31. The process of claim 29 wherein the metal amide is selected from the group consisting of tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tert-butylimino tris(diethylamino)tantalum (TBTDET), tert-butylimino tris(dimethylamino)tantalum (TBTDMT), tert-butylimino tris(ethylmethylamino)tantalum (TBTEMT), ethyllimino tris(diethylamino)tantalum (EITDET), ethyllimino tris(dimethylamino)tantalum (EITDMT), ethyllimino tris(ethylmethylamino)tantalum (EITEMT), tert-amylimino tris(dimethylamino)tantalum (TAIMAT), tert-amylimino tris(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amylimino tri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten, and mixture thereof.

32. The process of claim 29 is selected from the group consisting of an atomic layer deposition(ALD) process and a chemical vapor deposition (CVD) process, optionally with ammonia.

33. The process of claim 29 using an additional treatment step for final film densification or film annealing, is selected from the group consisting of thermal, ozone, plasma, UV and microwave.

34. An CVD process optionally with ammonia employing a mixture comprising of (A)a precursor selected from the group consisting of:

(a)

 

wherein M is a metal selected from Group 4 of the Periodic Table of the Elements and R^1-4 can be same or different selected from the group consisting of dialkylamide, difluoralkylamide, hydrogen, alkyl, alkoxy, fluoroalkoxy, fluoroalkyl and alkoxy, cycloaliphatic, and aryl with the additional provision that when R¹ and R² are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy, or fluoroalkyl, they can be connected to form a ring;

(b)

 

wherein M is a metal selected from Group 4 of the Periodic Table of the Elements and R^5-10 can be same or different selected from the group consisting of hydrogen, alkyl, alkoxy, fluoroalkyl alkoxy, fluoroalkoxy, cycloaliphatic, and aryl with the additional provision that when R⁵, R⁶, R⁹ and R¹⁰ are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy or fluoroalkyl, they can be connected to form a ring;

(c)

 

wherein M is a metal selected from Group 5 of the Periodic Table of the Elements and R^11-16 can be same or different selected from the group consisting of, hydrogen, alkyl, alkoxy, fluoroalkoxy, fluoroalkyl and cycloaliphatic, and aryl;

n=1,2, m=5−

2n, wherein when R¹¹, R¹², R¹⁵ and R¹⁶ are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy or fluoroalkyl they can be connected to form a ring; and

(d)

 

wherein M is a metal selected from Group 6 of the Periodic Table of the Elements and R^17-22 can be same or different selected from the group consisting of, hydrogen, alkyl, alkoxy, fluoroalkyl and alkoxy, cycloaliphatic, and aryl;

p=1,2,3, q=6−

2p, wherein when R¹⁷, R¹⁸, R²¹ and R²² are dialkylamide, difluoralkylamide, alkoxy, fluoroalkoxy, or fluoroalkyl and, they can be connected to form a ring.

and

(B)a metal amide metal selected from the group consisting of tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tert-butylimino tris(diethylamino)tantalum (TBTDET), tert-butylimino tris(dimethylamino)tantalum (TBTDMT), tert-butylimino tris(ethylmethylamino)tantalum (TBTEMT), ethyllimino tris(diethylamino)tantalum (EITDET), ethyllimino tris(dimethylamino)tantalum (EITDMT), ethyllimino tris(ethylmethylamino)tantalum (EITEMT), tert-amylimino tris(dimethylamino)tantalum (TAIMAT), tert-amylimino tris(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amylimino tri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten, and mixture thereof.