Cobalt-containing compounds, their synthesis, and use in cobalt-containing film deposition

Patent metadata

Field	Value
Publication number	US-9790247-B2
Application number	US-201414765098-A
Country	US
Kind code	B2
Filing date	Jan 31, 2014
Priority date	Jan 31, 2013
Publication date	Oct 17, 2017
Grant date	Oct 17, 2017

Abstract

Cobalt-containing compounds, their synthesis, and their use for the deposition of cobalt containing films are disclosed. The disclosed cobalt-containing compounds have one of the following formulae: wherein each of R 1 , R 2 , R 3 , R 4 and R 5 is independently selected from Hydrogen; halogen; linear, cyclic or branched hydrocarbons; primary amino ligands (—NHR); or secondary amino ligands (—NRR′), with R and R′ independently being H or a linear, cyclic or branched hydrocarbon, provided at least one of R 1 , R 2 , or R 3 in Formula I and R 4 or R 5 in Formula II is an amino ligand.

First claim

We claim:

1. A compound having one of the following formulae:

wherein each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from the group consisting of Hydrogen; a halogen; linear, cyclic or branched hydrocarbons; primary amino ligands (—NHR); and secondary amino ligands (—NRR′), with R and R′ independently being H, a linear, cyclic or branched hydrocarbon, or SiMe 3 provided at least one of R 1 , R 2 , or R 3 in Formula I and R 4 or R 5 in Formula II is an amino ligand.

2. The compound of claim 1 , wherein the Formula I compound includes one or two neutral adduct ligands selected from the group consisting of NMe 3 , NEt 3 , NiPr 3 , NMeEt 2 , NC 5 H 5 , OC 4 H 8 , Me 2 O, and Et 2 O.

3. The compound of claim 1 , wherein the compound has Formula I and is selected from the group consisting of (NMe 2 ) 3 SiCo(CO) 4 , SiH(NMe 2 ) 2 Co(CO) 4 , SiH 2 (NMe 2 )Co(CO) 4 , Si(NEt 2 ) 3 Co(CO) 4 , SiH(NEt 2 ) 2 Co(CO) 4 , SiH 2 (NEt 2 )Co(CO) 4 , Si(N-iPr 2 ) 3 Co(CO) 4 , SiH(N-iPr 2 ) 2 Co(CO) 4 , SiH 2 (N-iPr 2 )Co(CO) 4 , Si(NHtBu) 3 Co(CO) 4 , SiH(NHtBu) 2 Co(CO) 4 , SiH 2 (NHtBu)Co(CO) 4 , SiCl(NMe 2 ) 2 Co(CO) 4 , SiMe(NMe 2 ) 2 Co(CO) 4 , (CH 2 ═CH)Si(Me)(NMe 2 )Co(CO) 4 , (CH 2 ═CH)Si(Me)(NEt 2 )Co(CO) 4 , (CH 2 ═CH)Si(Me)(N-iPr 2 )Co(CO) 4 , (CH 2 ═CH)Si(NEt 2 ) 2 Co(CO) 4 , and (NHSiMe 3 )Si(Me)(H)Co(CO) 4 .

4. The compound of claim 3 , wherein the compound is selected from the group consisting of SiH(NEt 2 ) 2 Co(CO) 4 , Si(NMe 2 ) 3 Co(CO) 4 , SiH 2 (NiPr 2 )Co(CO) 4 , and SiH(NHtBu) 2 Co(CO) 4 .

5. The compound of claim 1 , wherein the compound has Formula II and is selected from the group consisting of (CO) 4 CoSi(NMe 2 ) 2 Co(CO) 4 , (CO) 4 CoSi(NEt 2 ) 2 Co(CO) 4 , (CO) 4 CoSi(N-iPr 2 ) 2 Co(CO) 4 , (CO) 4 CoSi(NMe 2 )(H)Co(CO) 4 , (CO) 4 CoSi(NEt 2 )(H)Co(CO) 4 , (CO) 4 CoSi(N-iPr 2 )(H)Co(CO) 4 , (CO) 4 CoSi(NHtBu)(H)Co(CO) 4 , (CO) 4 CoSi(NHSiMe 3 )(Me)Co(CO) 4 , (CO) 4 CoSi(NHSiMe 3 )(Et)Co(CO) 4 , (CO) 4 CoSi(NHSiMe 3 )(iPr)Co(CO) 4 , (CO) 4 CoSi(NHSiMe 3 )(tBu)Co(CO) 4 , (CO) 4 CoSi(CH═CH 2 )(NMe 2 )Co(CO) 4 , (CO) 4 CoSi(CH═CH 2 )(NEt 2 )Co(CO) 4 , (CO) 4 CoSi(CH═CH 2 )(N-iPr 2 )Co(CO) 4 , and (CO) 4 CoSi(CH═CH 2 )(NHtBu)Co(CO) 4 .

6. A method of depositing a cobalt-containing film, the method comprising:
introducing a cobalt-containing compound into a reactor having a substrate disposed therein, wherein the cobalt-containing compound has one of the formulae:

wherein each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from the group consisting of Hydrogen; a halogen; linear, cyclic or branched hydrocarbons; primary amino ligands (—NHR); and secondary amino ligands (—NRR′), with R and R′ independently being H or a linear, cyclic or branched hydrocarbon, provided at least one of R 1 , R 2 , or R 3 in Formula I and R 4 or R 5 in Formula II is an amino ligand;
depositing at least part of the cobalt-containing compound onto the substrate to form the cobalt-containing film.

7. The method of claim 6 , wherein the Formula I compound includes one or two neutral adduct ligands selected from the group consisting of NMe 3 , NEt 3 , NiPr 3 , NMeEt 2 , NC 5 H 5 , OC 4 H 8 , Me 2 O, and Et 2 O.

8. The method of claim 6 , wherein the cobalt containing compound has Formula I and is selected from the group consisting of (NMe 2 ) 3 SiCo(CO) 4 , SiH(NMe 2 ) 2 Co(CO) 4 , SiH 2 (NMe 2 )Co(CO) 4 , Si(NEt 2 ) 3 Co(CO) 4 , SiH(NEt 2 ) 2 Co(CO) 4 , SiH 2 (NEt 2 )Co(CO) 4 , Si(N-iPr 2 ) 3 Co(CO) 4 , SiH(N-iPr 2 ) 2 Co(CO) 4 , SiH 2 (N-iPr 2 )Co(CO) 4 , Si(NHtBu) 3 Co(CO) 4 , SiH(NHtBu) 2 Co(CO) 4 , SiH 2 (NHtBu)Co(CO) 4 , SiCl(NMe 2 ) 2 Co(CO) 4 , SiMe(NMe 2 ) 2 Co(CO) 4 , (CH 2 ═CH)Si(Me)(NMe 2 )Co(CO) 4 , (CH 2 ═CH)Si(Me)(NEt 2 )Co(CO) 4 , (CH 2 ═CH)Si(Me)(N-iPr 2 )Co(CO) 4 , (CH 2 ═CH)Si(NEt 2 ) 2 Co(CO) 4 , and (NHSiMe 3 )Si(Me)(H)Co(CO) 4 .

9. The method of claim 8 , wherein the cobalt containing compound is selected from the group consisting of SiH(NEt 2 ) 2 Co(CO) 4 , Si(NMe 2 ) 3 Co(CO) 4 , SiH 2 (NiPr 2 )Co(CO) 4 , and SiH(NHtBu) 2 Co(CO) 4 .

10. The method of claim 6 , wherein the cobalt containing compound has Formula II and is selected from the group consisting of (CO) 4 CoSi(NMe 2 ) 2 Co(CO) 4 , (CO) 4 CoSi(NEt 2 ) 2 Co(CO) 4 , (CO) 4 CoSi(N-iPr 2 ) 2 Co(CO) 4 , (CO) 4 CoSi(NMe 2 )(H)Co(CO) 4 , (CO) 4 CoSi(NEt 2 )(H)Co(CO) 4 , (CO) 4 CoSi(N-iPr 2 )(H)Co(CO) 4 , (CO) 4 CoSi(NHtBu)(H)Co(CO) 4 , (CO) 4 CoSi(NHSiMe 3 )(Me)Co(CO) 4 , (CO) 4 CoSi(NHSiMe 3 )(Et)Co(CO) 4 , (CO) 4 CoSi(NHSiMe 3 )(iPr)Co(CO) 4 , (CO) 4 CoSi(NHSiMe 3 )(tBu)Co(CO) 4 , (CO) 4 CoSi(CH═CH 2 )(NMe 2 )Co(CO) 4 , (CO) 4 CoSi(CH═CH 2 )(NEt 2 )Co(CO) 4 , (CO) 4 CoSi(CH═CH 2 )(N-iPr 2 )Co(CO) 4 , and (CO) 4 CoSi(CH═CH 2 )(NHtBu)Co(CO) 4 .

11. The method of claim 6 , wherein the depositing step is selected from the group consisting of chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma enhanced chemical vapor deposition (PECVD), plasma enhanced atomic layer deposition (PEALD), pulsed chemical vapor deposition (PCVD), low pressure chemical vapor deposition (LPCVD), sub-atmospheric chemical vapor deposition (SACVD), atmospheric pressure chemical vapor deposition (APCVD), spatial ALD, radicals incorporated deposition, super critical fluid deposition, and combinations thereof.

12. The method of claim 6 , wherein the method is performed at a temperature between about 20° C. and about 800° C., preferably between about 25° C. and about 600° C.

13. The method of claim 6 , wherein the reactor has a pressure between approximately 0.1 Pa and approximately 10 5 Pa, preferably between approximately 2.5 Pa and approximately 10 3 Pa.

14. The method of claim 6 , wherein the cobalt-containing film is selected from the group consisting of pure cobalt, cobalt nitride(CoN), cobalt silicide (CoSi), cobalt silicide nitride (CoSiN), and cobalt oxide(CoO).

15. The method of claim 6 , further comprising introducing a reaction gas into the reactor at the same time or at an alternate time as the introduction of the cobalt-containing compound.

16. The method of claim 15 , wherein the reaction gas is a reducing agent selected from the group consisting of N 2 , H 2 , NH 3 , SiH 4 , Si 2 H 6 , Si 3 H 8 , (Me) 2 SiH 2 , (C 2 H 5 ) 2 SiH 2 , (CH 3 ) 3 SiH, (C 2 H 5 ) 3 SiH, [N(C 2 H 5 ) 2 ] 2 SiH 2 , N(CH 3 ) 3 , N(C 2 H 5 ) 3 , (SiMe 3 ) 2 NH, (CH 3 )HNNH 2 , (CH 3 ) 2 NNH 2 , phenyl hydrazine, B 2 H 6 , (SiH 3 ) 3 N, radical species of these reducing agents, and mixtures of these reducing agents.

17. The method of claim 15 , wherein the reaction gas is an oxidizing reagent selected from the group consisting of O 2 , O 3 , H 2 O, H 2 O 2 , NO, NO 2 , acetic acid, radical species of these oxidizing agents, and mixtures of these oxidizing agents.

18. The compound of claim 3 , wherein the compound is (NMe 2 ) 3 SiCo(CO) 4 .

19. The compound of claim 3 , wherein the compound is SiH(NEt 2 ) 2 Co(CO) 4 .

20. The compound of claim 10 , wherein the compound is (CO) 4 CoSi(NEt 2 ) 2 Co(CO) 4 .

Assignees

• L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude

Inventors

• Gatineau Satoko
• Ko Changhee

Classifications

• H10P14/43

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

• H10D64/0112

  using conductive layers comprising silicides · CPC title

• H10W20/032

  of conductive barrier, adhesion or liner layers · CPC title

• C23C16/50

  using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)} · CPC title

• C23C16/45525

  Atomic layer deposition [ALD] · CPC title