# US 11,440,929 B2 · Bis(diazadiene)cobalt compounds, method of making and method of use thereof

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- Number: US 11,440,929 B2
- Document ID: US11440929B2
- Status: Granted
- Kind: B2
- Application number: 16/429,343
- Filed: 2019-06-03
- Published: 2019-12-19
- Granted: 2022-09-13
- Earliest claimed: 2018-06-19
- Assignees: Versum Materials US, LLC
- Applicants: Versum Materials US, LLC
- Inventors: Alan C. Cooper; Sergei V. Ivanov; Christopher David Hopkins; Moo-Sung Kim
- Web page: https://patentgrep.com/patent/US11440929B2

## CPC

- C07F 15/065: {without a metal-carbon linkage}
- C23C 16/18: from metallo-organic compounds
- C23C 16/4481: {by evaporation using carrier gas in contact with the source material (C23C16/4486 takes precedence)}
- C23C 16/453: passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD (C23C16/513 takes precedence; for flame or plasma spraying of coating material in the molten state C23C4/00)
- C23C 16/45536: {Use of plasma, radiation or electromagnetic fields}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/02: Pretreatment of the material to be coated (C23C16/04 takes precedence)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- 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)

## Abstract

Described herein are cobalt compounds, processes for making cobalt compounds, cobalt compounds used as precursors for depositing cobalt-containing films (e.g., cobalt, cobalt oxide, cobalt nitride, cobalt silicide etc.); and cobalt films. Examples of cobalt precursor compounds are bis(diazadiene)cobalt compounds. Examples of surfaces for deposition of metal-containing films include, but are not limited to, metals, metal oxides, metal nitrides, and metal silicates; silicon, silicon oxide and silicon nitride. Alkylated diazadiene ligands are used to form cobalt complexes which are used for selective deposition on certain surfaces and/or superior film properties such as uniformity, continuity, and low resistance.

## Claims

### Claim 1

A bis(diazadiene)cobalt compound having a structure selected from the group consisting of:
(a)
wherein R is tert-amyl;
wherein the bis(diazadienecobalt) compound comprises a non-volatile residue of less than, or equal to, 1.1 weight percent.

### Claim 2 (depends on 1)

The bis(diazadiene)cobalt compound of claim 1 has a melting point less than, or equal to, 80° C.

### Claim 3 (depends on 1)

The bis(diazadiene)cobalt compound of claim 1 exists at least in a liquid phase at a temperature greater than, or equal to, 40° C.

### Claim 4

A method of synthesizing a bis(diazadiene)cobalt compound, comprising:
adding a first alkyl amine to a diketone compound in a mixture of an organic solvent and water to obtain a diazadiene ligand;
reacting the diazadiene ligand with a cobalt halide in the presence of a reducing co-reagent to form a bis(diazadiene)cobalt compound;
wherein the bis(diazadiene)cobalt compound has a structure selected from the group consisting of:
(a)
wherein R is tert-amyl;
wherein the bis(diazadiene)cobalt compound comprises a non-volatile residue of less than, or equal to, 1.1 weight percent.

### Claim 5 (depends on 4)

The method of claim 4, wherein the first alkyl amine is tert-amyl; the cobalt halide is selected from the group consisting of cobalt chloride, cobalt bromide, and cobalt iodide; and the organic solvent is selected from the group consisting of hydrocarbon solvents, hexanes, tetrahydrofuran, diethyl ether, toluene, and combinations thereof.

### Claim 6 (depends on 4)

The method of claim 4, the bis(diazadiene)cobalt compound has a melting point less than, or equal to, 80° C.

### Claim 7 (depends on 4)

The method of claim 4, wherein the bis(diazadiene)cobalt compound exists at least in a liquid phase at a temperature greater than, or equal to, 40° C.

### Claim 8

A cobalt containing film deposited by using a bis(diazadiene)cobalt compound having a structure selected from the group consisting of:
(a)
wherein R is tert-amyl; and
wherein the bis(diazadiene)cobalt compound comprises a non-volatile residue of less than, or equal to, 1.1 weight percent;
wherein the cobalt containing film is selected from a group consisting of cobalt film, cobalt oxide film, cobalt silicide film, and cobalt nitride film; and
wherein the cobalt containing film is deposited by using a method selected from a group consisting of thermal CVD, thermal ALD, plasma-enhanced ALD (PEALD), plasma enhanced chemical vapor deposition (PECVD), and plasma enhanced cyclic chemical vapor deposition (PECCVD).

### Claim 9 (depends on 8)

The cobalt containing film of claim 8, wherein the bis(diazadiene)cobalt compound has a melting point less than or equal to 80° C.

### Claim 10 (depends on 8)

The cobalt containing film of claim 8, wherein the cobalt containing film contains less than 2.5 atomic percent of carbon or nitrogen.

### Claim 11 (depends on 8)

The cobalt containing film of claim 8, wherein the bis(diazadiene)cobalt compound exists at least in a liquid phase at a temperature greater than, or equal to, 40° C.

### Claim 12

A container comprising a bis(diazadiene)cobalt compound having a structure selected from the group consisting of:
(a)
wherein R is tert-amyl;
wherein the bis(diazadiene)cobalt compound comprises a non-volatile residue of less than, or equal to, 1.1 weight percent.

### Claim 13

The container of claim of 12, wherein the bis(diazadiene)cobalt compound has a melting point less than or equal to 80° C.

### Claim 14 (depends on 12)

The container of claim 12 is maintained at a delivery temperature, and the melting point of the bis(diazadiene)cobalt compound is lower than the delivery temperature.

### Claim 15

The container of claim of 26, wherein the bis(diazadiene)cobalt compound exists at least in a liquid phase at a temperature greater than, or equal to, 40° C.

### Claim 16

A method of depositing a Co containing film on a substrate in a reactor, comprising:
providing the substrate to the reactor;
providing a Co precursor to the reactor;
contacting the substrate with the Co precursor; and
forming the Co containing film on the substrate;
wherein the substrate is selected from the group consisting of metal, metal oxide, metal nitride, metal silicide, silicon, silicon oxide, silicon nitride, fluorosilicate glass (FSG), organosilicate glass (OSG), carbon doped oxide (CDO), porous low-K material, and combinations thereof; and
wherein the Co precursor is a bis(diazadiene)cobalt compound having a structure selected from the group consisting of:
(a)
wherein R is tert-amyl;
wherein the bis(diazadiene)cobalt compound comprises a non-volatile residue of less than, or equal to, 1.1 weight percent.

### Claim 17 (depends on 16)

The method of claim 16, wherein the Co containing film is selected from a group consisting of cobalt film, cobalt oxide film, cobalt silicide film, cobalt nitride film, and combinations thereof; and the Co containing film is deposited by a method selected from a group consisting of thermal CVD, thermal ALD, plasma-enhanced ALD (PEALD), plasma enhanced chemical vapor deposition (PECVD), and plasma enhanced cyclic chemical vapor deposition (PECCVD).

### Claim 18 (depends on 16)

The method of claim 16 wherein the bis(diazadiene)cobalt compound has a melting point less than, or equal to, 80° C.

### Claim 19 (depends on 16)

The method of claim 16, further comprising a step selected from the group consisting of a pre-treatment to remove contaminates from surface of the substrate, annealing with heating the Co containing film to 300-500° C. in the flow of a hydrogen containing gas, and a combination thereof.

### Claim 20 (depends on 16)

The method of claim 16, wherein the Co containing film contains less than 2.5 atomic percent of carbon or nitrogen.

### Claim 21 (depends on 16)

The method of claim 16, wherein the bis(diazadiene)cobalt compound exists at least in a liquid phase at a temperature greater than, or equal to, 40° C.

### Claim 22

A method of selectively depositing cobalt on a substrate in a reactor, comprising:
providing the substrate to the reactor wherein the substrate comprises at least one patterned dielectric layer and at least one patterned metal containing layer;
providing a Co precursor to the reactor;
contacting the substrate with the Co precursor; and
forming Co containing film on the substrate;
wherein the at least one patterned dielectric layer is selected from the group consisting of silicon dioxide, fluorosilicate glass (FSG), organosilicate glass (OSG), carbon doped oxide (CDO), porous low-K materials, and combinations thereof;
wherein at least one patterned metal containing layer is selected from the group consisting of conductive metal layer selected from the group consisting of copper or copper alloy, cobalt or cobalt alloy, ruthenium or ruthenium alloy; and combinations thereof; metal oxide; metal nitride; metal silicate layer; and combinations thereof;
wherein the Co containing film is selectively formed on the at least one patterned conductive metal layer with ratio of thickness of cobalt containing film formed on the at least one patterned conductive metal layer vs. formed on the at least one patterned dielectric layer >1; and
wherein the Co precursor is a bis(diazadiene)cobalt compound having a structure selected from the group consisting of:
(a)
wherein R is tert-amyl;
wherein the bis(diazadiene)cobalt compound comprises a non-volatile residue of less than, or equal to, 1.1 weight percent.

### Claim 23 (depends on 22)

The method of claim 22, wherein the bis(diazadiene)cobalt compound either has a melting point less than or equal to 80° C.

### Claim 24 (depends on 22)

The method of claim 22, wherein the cobalt-containing film thickness on the metal oxide, metal nitride, or metal silicide vs. the cobalt-containing film thickness on the at least one patterned dielectric layer is ≥10:1.

### Claim 25 (depends on 22)

The method of claim 22, further comprising a step selected from the group comprising a pre-treatment to remove contaminates from surface of the substrate, annealing with heating the Co containing film to 300-500° C. in the flow of a hydrogen containing gas, and a combination thereof.

### Claim 26 (depends on 22)

The method of claim 22, wherein the Co containing film contains less than 2.5 atomic percent of carbon or nitrogen.

### Claim 27 (depends on 22)

The method of claim 22, wherein the bis(diazadiene)cobalt compound exists at least in a liquid phase at a temperature greater than, or equal to, 40° C.