Adhesion to copper and copper electromigration resistance

1. A method for improving adhesion of a semiconductor device comprising steps of:

(a) providing a substrate in a processing chamber;

wherein the substrate comprises at least one patterned dielectric layer and at least one patterned conductive metal layer;

(ab) exposing the substrate to a pre-treatment; and

(b) introducing an organometallic precursor to the processing chamber to selectively deposit an adhesion layer on the at least one patterned conductive metal layer;

wherein

the organometallic precursor is selected from the group consisting of organozinc, organosilver, organochromium, organotin, organomanganese, organonickel, organocobalt , organoaluminum, and mixtures thereof; and

steps (ab) and (b) are repeated until a desired thickness of the adhesion layer is achieved.

2. The method in claim 1 , wherein the pre-treatment is selected from the group consisting of H 2 plasma, NH 3 plasma, H 2 /He plasma, H 2 /N 2 plasma and mixtures thereof.

3. The method in claim 1 further comprising a step (c) depositing a dielectric barrier layer on the substrate having the adhesion layer.

4. The method in claim 3 further comprising a step before (c):

exposing the substrate having the adhesion layer to a post-treatment.

5. The method in claim 3 , wherein the dielectric barrier layer is selected from the group consisting of: silicon nitride, silicon oxide, silicon oxycarbide, silicon oxynitride, silicon carbonitride, silicon oxycarbonitride, silicon carbide, and mixtures thereof.

6. The method of claim 3 wherein the dielectric barrier layer has a dielectric constant of less than 7.

7. The method in claim 4 , wherein the post-treatment is selected from the group consisting of H 2 plasma, NH 3 plasma, H 2 /He plasma , H 2 /N 2 plasma and mixtures thereof.

8. The method in claim 1 , wherein the organometallic precursor is solubilized in a solvent selected from the group consisting of a hydrocarbon with formula C n H (2n+2−x) ; where n is 3-10 and x is equal to the number of cyclic structures or the degrees of unsaturation; an oxygen containing solvents; and mixtures thereof;

wherein the solvent solubilizes the organometallic precursor without decomposing the organometallic precursor.

9. The method in claim 8 , wherein weight % of the solvent ranges from 5% to 99%.

10. The method in claim 8 , wherein weight % of the solvent ranges from 50% to 90%.

11. The method in claim 8 , wherein the oxygen containing solvent is selected from the group consisting of an ester, an alcohol, and mixtures thereof.

12. The method in claim 8 , wherein the hydrocarbon is selected from the group consisting of hexane, hexadiene, pentane, heptane, cyclohexane, cyclooctane, an aromatic hydrocarbon of the general structure C 6 H (6−b) R b , wherein R is 0-6, and mixtures thereof.

13. The method in claim 12 , wherein the aromatic hydrocarbon is selected from the group consisting of toluene, mesytelene, xylene, para-cymene and mixtures thereof.

14. The method in claim 1 , wherein the organometallic precursor is contained and delivered in a container comprising an interior volume bounded by interior wall, an inlet, and an outlet.

15. The method in claim 1 , wherein the organometallic precursor is contained and delivered at sub-atmospheric pressure in a pressurized container, comprising

(a) a valve body in sealed communication with an outlet orifice of the pressurized container, said outlet orifice of said pressurized container open to an interior chamber of said pressurized container;

(b) a fluid discharge path in the valve body, between the outlet orifice of the pressurized container and an outlet orifice of the valve body;

(c) a pressure regulator having a pressure sensing means capable of responding to sub-atmospheric pressure, integral to said valve body, in-line in the fluid discharge path, said pressure regulator pre-set to a pressure below atmospheric pressure to allow said gas to be delivered through said regulator from said interior chamber only when said pressure sensing means senses a downstream pressure at or below said pre-set pressure; and

(d) a high pressure shut-off valve integral to said valve body, in-line in the fluid discharge path and upstream from said pressure regulator; whereby said gas may flow through from said interior chamber of said pressurized container through said fluid discharge path, through said outlet orifice of said pressurized container, and through said outlet orifice of said valve body only when said outlet orifice is connected to a vacuum system.

16. The method of claim 1 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), a porous organosilicate glass having a dielectric constant of less than 3.0, and mixtures thereof.

17. The method of claim 1 wherein the at least one patterned dielectric layer has a dielectric constant of less than 3.2.

18. The method in claim 1 , wherein the at least one patterned conductive metal layer is selected from the group consisting of copper, copper alloys and mixtures thereof.

19. The method in claim 1 , wherein the organometallic precursor is selected from the group consisting of tetramethyltin (Me 4 Sn), dibutyldimethyltin, tributyltin hydride, tetraalkyltin, trialkyltin hydride, dialkyltin dihydride, alkylalkoxytin, tetraalkoxytin, tetrakis(dialkylamino)tin, tin hydride (SnH 4 ), tin deuteride (SnD 4 ), cyclopentadienyl cobalt dicarbonyl (CpCo(CO) 2 ), nitrosyl cobalt pentacarbonyl, cyclopentadienyl manganese tricarbonyl (CpMn(CO) 3 ), bis(ethylcyclopentadienyl)nickel ((EtCp) 2 Ni), diethylzinc (Et 2 Zn), diethylzinc-trimethylamine adduct, dimethylzinc, dialkylzinc, amine adducts of dialkylzinc, nickel hexacarbonyl (Ni(CO) 6 ), tungsten hexafluoride (WF 6 ), chromium hexacarbonyl (Cr(CO) 6 ), trimethylaluminum, dimethylethylamine alane (DMEAA) , tungsten hexacarbonyl (W(CO) 6 ), and mixtures thereof.

20. The method in claim 1 , wherein the adhesion layer is deposed by a process selected from the group consisting of Atomic Layer Deposition (ALD), Plasma Enhanced Atomic Layer Deposition (PEALD), Chemical Vapor Deposition(CVD), and Plasma Enhanced Chemical Vapor Deposition(PECVD), Low Pressure Chemical Vapor Deposition(LPCVD), Sub Atmospheric Chemical Vapor Deposition(SACVD), UV-assisted Chemical Vapor Deposition, Filament-assisted Chemical Vapor Deposition (FACVD), and Atmospheric Pressure Chemical Vapor Deposition (APCVD).

21. The method in claim 1 , wherein the adhesion layer is selected from the group consisting of tin and zinc.

22. The method of claim 1 , wherein the adhesion layer is tin.

23. A method for processing a semiconductor device having an improved adhesion comprising steps of:

(a) providing a substrate in a processing chamber;

wherein the substrate comprises at least one patterned dielectric layer and at least one patterned conductive metal layer;

(b exposing the substrate to a pre-treatment;

(c) introducing an organotin precursor to the processing chamber to selectively deposit an adhesion layer on the at least one patterned conductive metal layer after the pre-treatment in (b);

(d) exposing the substrate having the adhesion layer to a post-treatment; and

(e) depositing a dielectric barrier layer on the substrate having the adhesion layer after the post-treatment in (d).

24. The method in claim 23 , wherein steps (b), (c) and (d) are repeated until a desired thickness of the adhesion layer is achieved.

25. The method in claim 23 , wherein

the at least one patterned dielectric layer is selected from the group consisting of silicon dioxide, fluorosilicate galss (FSG), organosilicate glass (OSG), carbon doped oxide (CDO), a porous organosilicate glass having a dielectric constant of less than 3.0, and mixtures thereof;

the at least one patterned conductive metal layer is selected from the group consisting of copper , copper alloys, and mixtures thereof;

the pre-treatment and the post-treatment are both H 2 plasma; and

the organotin precursor is selected from the group consisting of Tetramethyltin (Me 4 Sn), dibutyldimethyltin, tributyltin hydride, tetraalkyltin, trialkyltin hydride, dialkyltin dihydride, alkylalkoxytin, tetraalkoxytin, tetrakis(dialkylamino)tin, tin hydride (SnH 4 ), tin deuteride (SnD 4 ), and mixtures thereof.

26. The method in claim 23 , wherein the organotin precursor is Tetramethyltin (Me 4 Sn).

27. The method in claim 23 , wherein the adhesion layer is deposed by a process selected from the group consisting of Atomic Layer Deposition (ALD), Plasma Enhanced Atomic Layer Deposition (PEALD), Chemical Vapor Deposition(CVD), and Plasma Enhanced Chemical Vapor Deposition(PECVD), Low Pressure Chemical Vapor Deposition(LPCVD), Sub Atmospheric Chemical Vapor Deposition(SACVD), UV-assisted Chemical Vapor Deposition, Filament-assisted Chemical Vapor Deposition (FACVD), and Atmospheric Pressure Chemical Vapor Deposition (APCVD).

28. The method in claim 23 , wherein the organotin precursor is solubilized in a solvent selected from the group consisting of a hydrocarbon with formula C n H (2n+2−x) ; where n is 3-10 and x is equal to the number of cyclic structures or the degrees of unsaturation; an oxygen containing solvents; and mixtures thereof;

wherein the solvent solubilizes the organometallic precursor without decomposing the organometallic precursor.

29. The method in claim 28 , wherein weight % of the solvent ranges from 5% to 99%.

30. The method in claim 28 , wherein weight % of the solvent ranges from 50% to 90%.

31. The method in claim 28 , wherein the oxygen containing solvent is selected from the group consisting of an ester, an alcohol, and mixtures thereof.

32. The method in claim 28 , wherein the hydrocarbon is selected from the group consisting of hexane, hexadiene, pentane, heptane, cyclohexane, cyclooctane, an aromatic hydrocarbon of the general structure C 6 H (6−b) R b , wherein R is 0-6; and mixtures thereof.

33. The method in claim 32 , wherein the aromatic hydrocarbon is selected from the group consisting of toluene, mesytelene, xylene, para-cymene and mixtures thereof.

34. The method in claim 28 , wherein the organotin precursor is tetramethyltin (Me 4 Sn) solubilized in hexane.

35. The method in claim 21 , wherein the organometallic precursor is contained and delivered in a container comprising an interior volume bounded by interior wall, an inlet, and an outlet.

36. The method in claim 23 , wherein the organotin precursor is contained and delivered at sub-atmospheric pressure in a pressurized container, comprising

(a) a valve body in sealed communication with an outlet orifice of the pressurized container, said outlet orifice of said pressurized container open to an interior chamber of said pressurized container;

(b) a fluid discharge path in the valve body, between the outlet orifice of the pressurized container and an outlet orifice of the valve body;

(c) a pressure regulator having a pressure sensing means capable of responding to sub-atmospheric pressure, integral to said valve body, in-line in the fluid discharge path, said pressure regulator pre-set to a pressure below atmospheric pressure to allow said gas to be delivered through said regulator from said interior chamber only when said pressure sensing means senses a downstream pressure at or below said pre-set pressure; and

(d) a high pressure shut-off valve integral to said valve body, in-line in the fluid discharge path and upstream from said pressure regulator; whereby said gas may flow through from said interior chamber of said pressurized container through said fluid discharge path, through said outlet orifice of said pressurized container, and through said outlet orifice of said valve body only when said outlet orifice is connected to a vacuum system.