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

Patent metadata

Field	Value
Publication number	US-2016010204-A1
Application number	US-201414765090-A
Country	US
Kind code	A1
Filing date	Jan 31, 2014
Priority date	Jan 31, 2013
Publication date	Jan 14, 2016
Grant date	—

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 the group consisting of hydrogen and linear, cyclic, or branched hydrocarbon groups; provided that (a) R 1 ≠R 2 and/or R 3 when R 1 and R 2 and R 3 are a hydrocarbon group; (b) R 1 and R 2 are a hydrocarbon group when R 3 is H; or (c) R 1 is a C2-C4 hydrocarbon group when R 2 and R 3 are H.

First claim

1 - 10 . (canceled)

11 . 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 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 and linear, cyclic, or branched hydrocarbon groups; provided that (a) R 1 , R 2 , and R 3 are a C2 to C4 hydrocarbon when R 1 ═R 2 ═R 3 , (b) R 1 and R 2 are a hydrocarbon group when R 3 is H, and (c) R 1 is a hydrocarbon group when R 2 and R 3 are H; and
depositing at least part of the cobalt-containing compound onto the substrate to form the cobalt-containing film.

12 . The method of claim 11 , 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.

13 . The method of claim 11 , wherein the cobalt-containing compound is selected from the group consisting of Et 3 SiCo(CO) 4 , nPr 3 SiCo(CO) 4 , iPr 3 SiCo(CO) 4 , nBu 3 SiCo(CO) 4 , sec-Bu 3 SiCo(CO) 4 , iBu 3 SiCo(CO) 4 , tBu 3 SiCo(CO) 4 , EtMeHSiCo(CO) 4 , nPrMeHSiCo(CO) 4 , iPrMeHSiCo(CO) 4 , PhMeHSiCo(C O ) 4 , Me 2 HSiCo(CO) 4 , Me 2 iPrSiCo(CO) 4 , Me 2 nPrSiCo(CO) 4 , Me 2 nBuSiCo(CO) 4 , Me 2 (sec-Bu)SiCo(CO) 4 , Me 2 tBuSiCo(CO) 4 , Me 2 iBuSiCo(CO) 4 , Me 2 PhSiCo(CO) 4 , Me 2 HSiCo(CO) 4 , Et 2 HSiCo(CO) 4 , Et 2 MeSiCo(CO) 4 , nPr 2 HSiCo(CO) 4 , iPr 2 HSiCo(CO) 4 , nBu 2 HSiCo(CO) 4 , sec-Bu 2 HSiCo(CO) 4 , iBu 2 HSiCo(CO) 4 , tBu 2 HSiCo(CO) 4 , Ph 2 HSiCo(CO) 4 , MeH 2 SiCo(CO) 4 , EtH 2 SiCo(CO) 4 , nPrH 2 SiCo(CO) 4 , iPrH 2 SiCo(CO) 4 , nBuH 2 SiCo(CO) 4 , sec-BuH 2 SiCo(CO) 4 , iBUH 2 SiCo(CO) 4 , tBUH 2 SiCo(CO) 4 , PhH 2 SiCo(CO) 4 , (CO) 4 CoSiH 2 CO(CO) 4 , (CO) 4 CoSiMe 2 Co(CO) 4 , (CO) 4 CoSiEt 2 Co(CO) 4 , (CO) 4 CoSi(iPr) 2 Co(CO) 4 , (CO) 4 CoSi(Ph) 2 Co(CO) 4 , and (CO) 4 CoSi(CH 2 ═CH)(H)Co(CO) 4 .

14 . The method of claim 13 , wherein the cobalt containing compound is selected from the group consisting of Et 2 HSiCo(CO) 4 , Et 3 SiCo(CO) 4 , and iPr 3 SiCo(CO) 4 .

15 . The method of claim 11 , 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.

16 . The method of claim 11 , 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.

17 . The method of claim 11 , 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.

18 . The method of claim 11 , 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).

19 . The method of claim 11 , 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.

20 . The method of claim 19 , 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.

21 . The method of claim 19 , 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.

22 . The method of claim 14 , wherein the cobalt containing compound is Et 3 SiCo(CO) 4 .

23 . 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 the following formula:

wherein each of R 1 , R 2 , and R 3 is independently selected from the group consisting of hydrogen and linear, cyclic, or branched hydrocarbon groups; provided that (a) R 1 , R 2 , and R 3 are a C2 to C4 hydrocarbon when R 1 ═R 2 ═R 3 , (b) R 1 and R 2 are a hydrocarbon group when R 3 is H, and (c) R 1 is a hydrocarbon group when R 2 and R 3 are H;
introducing a reaction gas into the reactor at the same time or at an alternate time as the introduction of the cobalt-containing compound; and
depositing at least part of the cobalt-containing compound onto the substrate to form the cobalt-containing film.

24 . The method of claim 23 , wherein the cobalt-containing compound is selected from the group consisting of Et 3 SiCo(CO) 4 , nPr 3 SiCo(CO) 4 , iPr 3 SiCo(CO) 4 , nBu 3 SiCo(CO) 4 , sec-Bu 3 SiCo(CO) 4 , iBu 3 SiCo(CO) 4 , tBu 3 SiCo(CO) 4 , EtMeHSiCo(CO) 4 , nPrMeHSiCo(CO) 4 , iPrMeHSiCo(CO) 4 , PhMeHSiCo(C O ) 4 , Me 2 HSiCo(CO) 4 , Me 2 iPrSiCo(CO) 4 , Me 2 nPrSiCo(CO) 4 , Me 2 nBuSiCo(CO) 4 , Me 2 (sec-Bu)SiCo(CO) 4 , Me 2 tBuSiCo(CO) 4 , Me 2 iBuSiCo(CO) 4 , Me 2 PhSiCo(CO) 4 , Me 2 HSiCo(CO) 4 , Et 2 HSiCo(CO) 4 , Et 2 MeSiCo(CO) 4 , nPr 2 HSiCo(CO) 4 , iPr 2 HSiCo(CO) 4 , nBu 2 HSiCo(CO) 4 , sec-Bu 2 HSiCo(CO) 4 , iBu 2 HSiCo(CO) 4 , tBu 2 HSiCo(CO) 4 , Ph 2 HSiCo(CO) 4 , MeH 2 SiCo(CO) 4 , EtH 2 SiCo(CO) 4 , nPrH 2 SiCo(CO) 4 , iPrH 2 SiCo(CO) 4 , nBuH 2 SiCo(CO) 4 , sec-BuH 2 SiCo(CO) 4 , iBuH 2 SiCo(CO) 4 , tBuH 2 SiCo(CO) 4 , and PhH 2 SiCo(CO) 4 .

25 . The method of claim 24 , wherein the cobalt containing compound is selected from the group consisting of Et 2 HSiCo(CO) 4 , Et 3 SiCo(CO) 4 , and iPr 3 SiCo(CO) 4 .

26 . The method of claim 25 , wherein the cobalt containing compound is Et 3 SiCo(CO) 4 .

27 . The method of claim 23 , 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.

28 . The method of claim 27 , wherein the reaction gas is H 2 and NH 3 .

Assignees

• Air Liquide

Inventors

• Gatineau Satoko
• Ko Changhee
• Girard Jean-Marc
• Gatineau Julien

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

• C07F15/06 Primary

  Cobalt compounds · CPC title

• C23C16/40

  Oxides · CPC title