Cobalt deposition selectivity on copper and dielectrics
A process for forming cobalt on a substrate, comprising: volatilizing a cobalt precursor of the disclosure, to form, a precursor vapor: and contacting the precursor vapor with the substrate under vapor deposition conditions effective for depositing cobalt on the substrate from the precursor vapor, wherein the vapor deposition conditions include temperature not exceeding 200° C., wherein: the substrate includes copper surface and dielectric material, e.g., ultra-low dielectric material. Such cobalt deposition process can be used to manufacture product articles in which the deposited cobalt forms a capping layer, encapsulating layer, electrode, diffusion layer, or seed for electroplating of metal thereon, e.g., a semiconductor device, flat-panel, display, or solar panel. A cleaning composition containing base and oxidizing agent components may be employed to clean the copper prior to deposition of cobalt thereon, to achieve substantially reduced defects in the deposited cobalt.
1. A surface-selective deposition process for depositing cobalt on a having a copper surface, comprising:
cleaning the copper surface with an acid solution prior to vapor deposition of the deposited cobalt on the substrate, the acid solution having pH in a range of from 0 to 4;
cleaning the copper surface with a cleaning solution prior to vapor deposition of the deposited cobalt on the substrate, the cleaning solution comprising base and an oxidizing agent and having a pH in a range of from 5 to 10;
volatilizing a non-oxygen-containing cobalt precursor to form a precursor vapor, wherein the non-oxygen-containing cobalt precursor comprises a cobalt bis-diazadiene compound whose diazadiene moieties are optionally independently substituted on nitrogen and/or carbon atoms thereof with substituents selected from the group consisting of: H; C 1 -C 8 alkyl; C 6 -C 10 aryl; C 7 -C 16 alkylaryl; C 7 -C 16 arylalkyl; halo; amines; amidinates; guanidinates; and cyclopentadienyls, optionally substituted with C 1 -C 8 alkyl, amines, or halo substituents; and
contacting the precursor vapor with the substrate under vapor deposition conditions effective for depositing cobalt on the substrate from the precursor vapor, wherein the vapor deposition conditions include temperature not exceeding 200° C., and wherein the substrate includes copper surface and dielectric material surface and wherein cobalt is deposited selectively on the copper surface relative to the dielectric material.
2. The process of claim 1 , wherein the non-oxygen-containing cobalt precursor comprises a precursor selected from the group consisting of cobalt bis-diazadiene compounds whose diazadiene moieties are optionally independently substituted on nitrogen and/or carbon atoms thereof with substituents selected from the group consisting of: H; C 1 -C 8 alkyl; C 6 -C 10 aryl; C 7 -C 16 alkylaryl; C 7 -C 16 arylalkyl; halo; amines; amidinates; guanidinates; and cyclopentadienyls, optionally substituted with C 1 -C 8 alkyl, amines, or halo substituents.
3. The process of claim 1 , wherein the non-oxygen-containing cobalt precursor comprises a precursor selected from the group consisting of cobalt bis-diazadiene compounds whose diazadiene moieties are optionally independently substituted on nitrogen and/or carbon atoms thereof with substituents selected from the group consisting of: H; C 1 -C 8 alkyl; C 6 -C 10 aryl; C 7 -C 16 alkylaryl; C 7 -C 16 arylalkyl; halo; amines; amidinates; guanidinates; and cyclopentadienyls, optionally substituted with C 1 -C 8 alkyl, amines, or halo substituents.
4. The process of claim 1 , wherein the non-oxygen-containing cobalt precursor comprises:
5. The process of claim 1 , wherein the non-oxygen-containing cobalt precursor comprises a cobalt precursor of the formula {RNCHCHNR} 2 Co, or {R′NCRCRNR′} 2 Co, wherein each R and R′ is independently selected from among C 1 -C 8 alkyl.
6. The process of claim 1 , wherein the precursor vapor is mixed with hydrogen for said contacting.
7. The process of claim 1 , further comprising annealing the cobalt deposited on the substrate.
8. The process of claim 1 , wherein the non-oxygen-containing cobalt precursor comprises a cobalt precursor with mono- or bis-substituted alkyl-1,3-diazabutadienyl ligands.
9. The process of claim 1 , wherein the deposited cobalt forms an electrode.
10. The process of claim 1 , wherein said vapor deposition conditions comprise a deposition pressure in a range of from 2 to 1200 torr.
11. The process of claim 1 , further comprising annealing the cobalt deposited on the substrate by thermal annealing at temperature in a range of from 200° C. to 600° C.
12. The process of claim 1 , wherein said contacting of the precursor vapor with the substrate is carried out for a period of time sufficient to deposit cobalt on the substrate at a thickness in a range of from 2 nm to 1000 nm.
13. The process of claim 1 , wherein the cobalt deposited on the substrate has a resistivity in a range of from 7 to 48 μΩ-cm.
14. The process of claim 1 , wherein the deposited cobalt fills a via of the substrate and is deposited over the copper surface in the via.
15. The process of claim 1 , wherein the copper surface has one or more layers deposited thereon, and said cobalt is deposited on an outermost surface of said one or more layers.
16. The process of claim 1 , wherein the vapor deposition conditions include temperature in a range of from 120° C. to 175° C.