Selective bottom-up metal feature filling for interconnects

1. A method of forming a semiconductor device, the method comprising:

providing a substrate containing a patterned dielectric layer having a recessed feature with dielectric layer surfaces and a metal-containing surface on a bottom of the recessed feature;

reacting the dielectric layer surfaces with a reactant gas containing a hydrophobic functional group to form hydrophobic dielectric layer surfaces; and

filling the recessed feature with a metal in a bottom-up gas phase deposition process that hinders deposition of the metal on the hydrophobic dielectric layer surfaces, wherein the metal is selected from the group consisting of ruthenium (Ru), cobalt (Co), aluminum (Al), iridium (Ir), rhodium (Rh), osmium (Os), palladium (Pd), platinum (Pt), nickel (Ni), and a combination thereof, and wherein the filling the recessed feature with the metal overfills the recessed feature with the metal.

2. The method of claim 1 , wherein the reactant gas includes a silicon-containing gas.

3. The method of claim 2 , wherein the silicon-containing gas is selected from the group consisting of an alkyl silane, an alkoxysilane, an alkyl alkoxysilane, an alkyl siloxane, an alkoxysiloxane, an alkyl alkoxysiloxane, an aryl silane, an acyl silane, an aryl siloxane, an acyl siloxane, a silazane, and a combination thereof.

4. The method of claim 2 , wherein the reactant gas is selected from the group consisting of dimethylsilane dimethylamine (DMSDMA), trimethylsilane dimethylamine (TMSDMA), bis(dimethylamino) dimethylsilane (BDMADMS), N,O bistrimethylsilyltrifluoroacetamide (BSTFA), trimethylsilyl-pyrrole (TMS-pyrrole), and a combination thereof.

5. The method of claim 1 , wherein the metal-containing surface contains copper (Cu), tungsten (W), ruthenium (Ru), cobalt (Co), titanium nitride (TiN), tantalum nitride (TaN), or combinations thereof.

6. The method of claim 1 , wherein the metal is deposited by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

7. The method of claim 1 , wherein the metal includes ruthenium (Ru) metal and the Ru metal is deposited using a deposition gas containing Ru 3 (CO) 12 precursor vapor and CO carrier gas.

8. The method of claim 1 , wherein the metal includes ruthenium (Ru) metal and the Ru metal is deposited using a deposition gas containing Ru 3 (CO) 12 , (2,4-dimethylpentadienyl) (ethylcyclopentadienyl) ruthenium (Ru(DMPD)(EtCp)), bis(2,4-dimethylpentadienyl) ruthenium (Ru(DMPD) 2 ), (2,4-dimethylpentadienyl) (methylcyclopentadienyl) ruthenium, or a combination of two or more thereof.

9. The method of claim 1 , wherein the metal includes cobalt (Co) metal.

10. The method of claim 1 , wherein the metal includes cobalt (Co) metal and the Co metal is deposited using a deposition gas containing Co 2 (CO) 8 , Co 4 (CO) 12 , CoCp(CO) 2 , Co(CO) 3 (NO), Co 2 (CO) 6 (HCC t Bu), Co(acac) 2 , Co(Cp) 2 , Co(Me 5 Cp) 2 ), Co(EtCp) 2 , cobalt(II) hexafluoroacetylacetonate hydrate, cobalt tris(2,2,6,6-tetramethyl-3,5-heptanedionate), cobalt(III) acetylacetonate, bis(N,N′-diisopropylacetamidinato) cobalt, tricarbonyl allyl cobalt, or a combination of two or more thereof.

11. The method of claim 1 , wherein a diameter of the recessed feature is between about 10 nm and about 25 nm.

12. The method of claim 1 , wherein the dielectric layer includes a low-k dielectric material.

13. A method of forming a semiconductor device, the method comprising:

providing a substrate containing a patterned dielectric layer having a recessed feature with dielectric layer surfaces and a metal-containing surface on a bottom of the recessed feature;

reacting the dielectric layer surfaces with a silicon-containing reactant gas containing a hydrophobic functional group to form hydrophobic dielectric layer surfaces; and

filling the recessed feature with ruthenium (Ru) metal in a bottom-up gas phase deposition process that hinders deposition of the Ru metal on the hydrophobic dielectric layer surfaces, wherein the Ru metal is deposited in a chemical vapor deposition process using a deposition gas containing Ru 3 (CO) 12 precursor vapor and CO carrier gas, wherein the filling the recessed feature with the Ru metal overfills the recessed feature with the Ru metal.

14. The method of claim 13 , wherein the metal-containing surface contains copper (Cu), tungsten (W), ruthenium (Ru), cobalt (Co), titanium nitride (TiN), tantalum nitride (TaN), or combinations thereof.

15. A method of forming a semiconductor device, the method comprising:

providing a substrate containing a patterned dielectric layer having a recessed feature with dielectric layer surfaces and a metal-containing surface on a bottom of the recessed feature;

reacting the dielectric layer surfaces with a silicon-containing reactant gas containing a hydrophobic functional group to form hydrophobic dielectric layer surfaces; and

filling the recessed feature with cobalt (Co) metal in a bottom-up gas phase deposition process that hinders deposition of the Co metal on the hydrophobic dielectric layer surfaces, wherein the Co metal is deposited in a chemical vapor deposition process using a deposition gas containing a Co-containing precursor vapor, and wherein the filling the recessed feature recessed feature with the Co metal overfills the recessed feature with the Co metal.

16. The method of claim 15 , wherein the deposition gas contains Co 2 (CO) 8 , Co 4 (CO) 12 , CoCp(CO) 2 , Co(CO) 3 (NO), Co 2 (CO) 6 (HCC t Bu), Co(acac) 2 , Co(Cp) 2 , Co(Me 5 Cp) 2 ), Co(EtCp) 2 , cobalt(II) hexafluoroacetylacetonate hydrate, cobalt tris(2,2,6,6-tetramethyl-3,5-heptanedionate), cobalt(III) acetylacetonate, bis(N,N′-diisopropylacetamidinato) cobalt, tricarbonyl allyl cobalt, or a combination of two or more thereof.