# US 10,309,010 B2 · Cobalt-containing compounds, their synthesis, and use in cobalt-containing film deposition

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- Number: US 10,309,010 B2
- Document ID: US10309010B2
- Status: Granted
- Kind: B2
- Application number: 14/765,090
- Filed: 2014-01-31
- Published: 2016-01-14
- Granted: 2019-06-04
- Earliest claimed: 2013-01-31
- Assignees: L'Air Liquide, Societe Anonyme pour l'Etude et l'Exploitation des Procedes Georges Claude
- Applicants: L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude; Satoko Gatineau; Changhee Ko; Jean-Marc Girard; Julien Gatineau
- Inventors: Satoko Gatineau; Changhee Ko; Jean-Marc Girard; Julien Gatineau
- Web page: https://patentgrep.com/patent/US10309010B2

## CPC

- C23C 16/06: characterised by the deposition of metallic material
- C07F 15/06: Cobalt compounds
- C23C 16/18: from metallo-organic compounds
- C23C 16/28: Deposition of only one other non-metal element
- C23C 16/34: Nitrides {(C23C16/303 takes precedence)}
- C23C 16/40: Oxides
- C23C 16/406: {of iron group metals}
- C23C 16/42: Silicides
- C23C 16/45525: {Atomic layer deposition [ALD]}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- H10D 64/0112: {using conductive layers comprising silicides}
- H10P 14/43: Chemical deposition, e.g. chemical vapour deposition [CVD]
- H10W 20/032: {of conductive barrier, adhesion or liner layers}
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## 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 R1, R2, R3, R4 and R5 is independently selected from the group consisting of hydrogen and linear, cyclic, or branched hydrocarbon groups; provided that (a) R1≠R2 and/or R3 when R1 and R2 and R3 are a hydrocarbon group; (b) R1 and R2 are a hydrocarbon group when R3 is H; or (c) R1 is a C2-C4 hydrocarbon group when R2 and R3 are H.

## Claims

### Claim 1

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 R1, R2, R3, R4, and R5 is independently selected from the group consisting of hydrogen and linear, cyclic, or branched hydrocarbon groups; provided that (a) R1, R2, and R3 are a C2 to C4 hydrocarbon when R1═R2═R3, (b) R1 and R2 are a hydrocarbon group when R3 is H, or (c) R1 is a hydrocarbon group when R2 and R3 are H; and
depositing at least part of the cobalt-containing compound onto the substrate to form the cobalt-containing film.

### Claim 2 (depends on 1)

The method of claim 1, wherein the Formula I compound includes one or two neutral adduct ligands selected from the group consisting of NMe3, NEt3, NiPr3, NMeEt2, NC5H5, OC4H8, Me2O, and Et2O.

### Claim 3 (depends on 1)

The method of claim 1, wherein the cobalt-containing compound is selected from the group consisting of Et3SiCo(CO)4, nPr3SiCo(CO)4, iPr3SiCo(CO)4, nBu3SiCo(CO)4, sec-Bu3SiCo(CO)4, iBu3SiCo(CO)4, tBu3SiCo(CO)4, EtMeHSiCo(CO)4, nPrMeHSiCo(CO)4, iPrMeHSiCo(CO)4, PhMeHSiCo(Co)4, Me2HSiCo(CO)4, Me2iPrSiCo(CO)4, Me2nPrSiCo(CO)4, Me2nBuSiCo(CO)4, Me2(sec-Bu)SiCo(CO)4, Me2tBuSiCo(CO)4, Me2iBuSiCo(CO)4, Me2PhSiCo(CO)4, Me2HSiCo(CO)4, Et2HSiCo(CO)4, Et2MeSiCo(CO)4, nPr2HSiCo(CO)4, iPr2HSiCo(CO)4, nBu2HSiCo(CO)4, sec-Bu2HSiCo(CO)4, iBu2HSiCo(CO)4, tBu2HSiCo(CO)4, Ph2HSiCo(CO)4, MeH2SiCo(CO)4, EtH2SiCo(CO)4, nPrH2SiCo(CO)4, iPrH2SiCo(CO)4, nBuH2SiCo(CO)4, sec-BuH2SiCo(CO)4, iBUH2SiCo(CO)4, tBUH2SiCo(CO)4, PhH2SiCo(CO)4, (CO)4CoSiH2CO(CO)4, (CO)4CoSiMe2Co(CO)4, (CO)4CoSiEt2Co(CO)4, (CO)4CoSi(iPr)2Co(CO)4, (CO)4CoSi(Ph)2Co(CO)4, and (CO)4CoSi(CH2═CH)(H)Co(CO)4.

### Claim 4 (depends on 3)

The method of claim 3, wherein the cobalt containing compound is selected from the group consisting of Et2HSiCo(CO)4, Et3SiCo(CO)4, and iPrH3SiCo(CO)4.

### Claim 5 (depends on 4)

The method of claim 4, wherein the cobalt containing compound is Et3SiCo(CO)4.

### Claim 6 (depends on 1)

The method of claim 1, 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.

### Claim 7 (depends on 1)

The method of claim 1, wherein the method is performed at a temperature between 20° C. and 800° C.

### Claim 8 (depends on 1)

The method of claim 1, wherein the reactor has a pressure between 0.1 Pa and 105 Pa.

### Claim 9 (depends on 1)

The method of claim 1, 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).

### Claim 10 (depends on 1)

The method of claim 1, 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.

### Claim 11 (depends on 10)

The method of claim 10, wherein the reaction gas is a reducing agent selected from the group consisting of N2, H2, NH3, SiH4, Si2H6, Si3H8, (Me)2SiH2, (C2H5)2SiH2, (CH3)3SiH, (C2H5)3SiH, [N(C2H5)2]2SiH2, N(CH3)3, N(C2H5)3, (SiMe3)2NH, (CH3)HNNH2, (CH3)2NNH2, phenyl hydrazine, B2H6, (SiH3)3N, radical species of these reducing agents, and mixtures of these reducing agents.

### Claim 12 (depends on 10)

The method of claim 10, wherein the reaction gas is an oxidizing reagent selected from the group consisting of O2, O3, H2O, H2O2, NO, NO2, acetic acid, radical species of these oxidizing agents, and mixtures of these oxidizing agents.

### Claim 13

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 R1, R2, and R3 is independently selected from the group consisting of hydrogen and linear, cyclic, or branched hydrocarbon groups; provided that (a) R1, R2, and R3 are a C2 to C4 hydrocarbon when R1═R2═R3, (b) R1 and R2 are a hydrocarbon group when R3 is H, or (c) R1 is a hydrocarbon group when R2 and R3 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.

### Claim 14 (depends on 13)

The method of claim 13, wherein the cobalt-containing compound is selected from the group consisting of Et3SiCo(CO)4, nPr3SiCo(CO)4, iPr3SiCo(CO)4, nBu3SiCo(CO)4, sec-Bu3SiCo(CO)4, iBu3SiCo(CO)4, tBu3SiCo(CO)4, EtMeHSiCo(CO)4, nPrMeHSiCo(CO)4, iPrMeHSiCo(CO)4, PhMeHSiCo(CO)4, Me2HSiCo(CO)4, Me2iPrSiCo(CO)4, Me2nPrSiCo(CO)4, Me2nBuSiCo(CO)4, Me2(sec-Bu)SiCo(CO)4, Me2tBuSiCo(CO)4, Me2iBuSiCo(CO)4, Me2PhSiCo(CO)4, Me2HSiCo(CO)4, Et2HSiCo(CO)4, Et2MeSiCo(CO)4, nPr2HSiCo(CO)4, iPr2HSiCo(CO)4, nBu2HSiCo(CO)4, sec-Bu2HSiCo(CO)4, iBu2HSiCo(CO)4, tBu2HSiCo(CO)4, Ph2HSiCo(CO)4, MeH2SiCo(CO)4, EtH2SiCo(CO)4, nPrH2SiCo(CO)4, iPrH2SiCo(CO)4, nBuH2SiCo(CO)4, sec-BuH2SiCo(CO)4, iBuH2SiCo(CO)4, tBuH2SiCo(CO)4, and PhH2SiCo(CO)4.

### Claim 15 (depends on 14)

The method of claim 14, wherein the cobalt containing compound is selected from the group consisting of Et2HSiCo(CO)4, Et3SiCo(CO)4, and iPr3SiCo(CO)4.

### Claim 16 (depends on 15)

The method of claim 15, wherein the cobalt containing compound is Et3SiCo(CO)4.

### Claim 17 (depends on 13)

The method of claim 13, wherein the reaction gas is a reducing agent selected from the group consisting of N2, H2, NH3, SiH4, Si2H6, Si3H8, (Me)2SiH2, (C2H5)2SiH2, (CH3)3SiH, (C2H5)3SiH, [N(C2H5)2]2SiH2, N(CH3)3, N(C2H5)3, (SiMe3)2NH, (CH3)HNNH2, (CH3)2NNH2, phenyl hydrazine, B2H6, (SiH3)3N, radical species of these reducing agents, and mixtures of these reducing agents.

### Claim 18 (depends on 17)

The method of claim 17, wherein the reaction gas is H2 and NH3.